Substituted 5-aryl-2-(2-hydroxyphenyl)-2h-benzotriazole UV absorbers, compositions stabilized therewith and process for preparation thereof

ABSTRACT

where R is an aryl moiety, such as phenyl, naphthyl or biphenylyl, or is phenyl substituted by one or more trifluoromethyl, bromo or cyano, and E 1  and E 2  are independently hydrogen, alkyl, aralkyl and the like are prepared by reaction of a benzotriazole substituted on the 5-position of the benzo ring by a halogen atom with a arylboronic acid or ester in the presence of a transition-metal catalyst, such as palladium (II) diacetate. The benzotriazole compounds of formula I are particularly efficacious as stabilizers for automotive coatings and candle wax.

This is a divisional of application Ser. No. 10/417,999, filed Apr. 17,2003, now U.S. Pat. No. 6,703,510, which is a divisional of applicationSer. No. 09/722,876, filed Nov. 27, 2000, now U.S. Pat. No. 6,649,770.

The instant invention pertains to novel 5-aryl substituted benzotriazoleUV absorbers, to a novel process for their preparation and tocompositions stabilized by said benzotriazoles.

BACKGROUND OF THE INVENTION

The benzotriazoles have long been an important class of UV absorbers andhave gained wide commercial importance and acceptance for manyindustrial applications. The prior art is replete with references totheir manufacture and utility. However, as requirements become ever morestringent and demanding, the search for still more stable and durablebenzotriazoles continues. The gradual phase out of HAPS solvents, suchas xylene, because of environmental concerns and their replacement withnon-HAPS solvents, such as esters, ethers or ketones, and increaseddurability requirements for automotive coatings make this search moreurgent. Indeed, the automotive industry is most concerned about UVAlosses from automotive paints and coatings as seen in the publication byJ. L. Gerlock et al., Proc. 36th Annual Tech. Sym. (Cleveland CoatingSociety), May 18, 1993.

U.S. Pat. Nos. 4,226,763; 4,278,589; 4,315,848; 4,275,004; 4,347,180;5,554,760; 5,563,242; 5,574,166 and 5,607,987 describe selectedbenzotriazoles, substituted in the 3-position of the hydroxyphenyl ringby an α-cumyl group, which show very good durability in automotivecoatings. These benzotriazoles represent the present state of the art.The instant invention is directed at preparing benzotriazoles whichexhibit still better durability and low loss rates from the prior artbenzotriazoles.

U.S. Pat. Nos. 5,278,314; 5,280,124; 5,436,349 and 5,516,914 describered-shifted benzotriazoles. These benzotriazoles are substituted in the3-position of the phenyl ring with an α-cumyl group and at the5-position of the benzo ring by thio ethers, alkylsulfonyl orphenylsulfonyl moieties. Red-shifting the benzotriazoles is desirablefor spectral reasons. A group at the 5-position which is also electronwithdrawing provides additional benefits in low loss rates anddurability as found in the instant invention. Missing from these patentsare any alkylsulfones with seven or fewer carbon atoms. When suchsulfonyl substituents are combined with specifically α-cumyl moieties,extremely durable compounds result which, due to the bulk of the α-cumylmoiety have sufficiently low volatility to be useful in coating andother polymer systems.

The presence of an α-cumyl or phenyl group ortho to the hydroxy group onthe phenyl ring exerts a surprisingly large positive effect onbenzotriazole photostability in coatings and photographic gel systems.The magnitude of this effect, particularly when compared to a tert-butylgroup in that position, is well beyond prediction. The combination ofboth an electron withdrawing group on the benzo ring and an α-cumyl orphenyl group on the phenyl ring in the same molecule leads to extremelydesirable properties in coating systems when high UV absorber permanenceis critical.

Novel compounds meeting these parameters as being extremely stable inaggressive use environments constitute a first portion of thisinvention.

The presence of the electron withdrawing moiety at the 5-position of thebenzo ring has a powerful stabilizing effect on benzotriazoles ingeneral and is observed in other polymer systems such as polycarbonateand poly(vinyl chloride) substrates as well. However, the effect ofhaving an α-cumyl or phenyl group ortho to the hydroxy moiety on thephenyl ring is much smaller to non-existent in some polymer systems suchas polycarbonate or poly(vinyl chloride) even though critical forcoating systems as described above.

In addition to being more photostable, the compounds of this inventionare red-shifted, absorbing strongly in the 350–400 nm wavelength range.While such red-shifting is desirable in that a greater portion of the UVspectrum is absorbed, this can also introduce color if the absorptionbeyond 400 nm is significant. This can limit the use of such compounds,particularly in systems such as polycarbonate glazing applications orpresent difficulties in various pigmented systems.

It is found that the nature of the substituent ortho to the hydroxylgroup on the phenyl ring has an unexpected impact on color imparted tothe substrate by the benzotriazole. Thus, relatively subtle differencesin substitution on the phenyl ring can have a large impact on theresulting color and the applicability of the benzotriazole in specificcolor sensitive applications. There are striking differences betweenhaving hydrogen, alkyl or α-cumyl at this 3-position.

Furthermore, U.S. Pat. No. 5,977,219 teaches that, when the 5-positionof the benzo ring is substituted with a trifluoromethyl group, theresulting benzotriazole not only exhibits the same or greater enhancedstability when incorporated into thermoplastic resins, but also impartsless color than related benzotriazoles substituted at the 5-positionwith other electron withdrawing moieties such as sulfonyl or carbonyl.These trifluoromethyl compounds also absorb strongly in the 350–400 nmwavelength range despite the low color and are extremely compatible in awide range of substrates such as acrylic resins, hydrocarbons,polycarbonates and poly(vinyl chloride).

There are a multitude of general references to benzotriazoles having inthe 5-position of the benzo ring electron withdrawing groups such asesters, amides, sulfones and the like that are not substituted in the3-position of the phenyl ring by an α-cumyl or phenyl moiety. In many ofthese references the broadly described compounds are unexemplified andno teaching or appreciation taught of the positive effect onphotostability described in this invention. In any event, the vastmajority of these structures fall well outside the scope of instantinvention.

Japanese 1996-299547 discloses the use of heterocyclic compounds asnon-aqueous electrolytes for lithium batteries. These heterocycliccompounds included benzotriazoles substituted on the benzo ring byhydrogen, methyl, ethyl, amino, hydroxyl, 2-pyridyl or phenyl; andsubstituted on the hydroxyphenyl ring by at the 5-position by a methylgroup and at the 3-position by hydrogen, methyl, ethyl, amino, hydroxyl,2-pyridyl or phenyl.

U.S. Pat. No. 4,396,712 describes generically benzotriazole compoundswhich are substituted at the 5-position of the benzo ring by phenyl aslight stabilizers for photothermographic film. The only compounddisclosed specifically is5-phenyl-2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole. Thebenzotriazole UV absorbers provide improved storage stability bystabilizing the silver salts (oxidizing agents) in these dry imageforming materials. Only selected low molecular weight benzotriazoles aresuitable since the benzotriazole must be compatible with othercomponents of the image forming materials.

A. Suzuki, Pure & Applied Chem., 66, No. 2, 213 (1994) describes a newsynthetic method involving the reaction of sterically hindered arylboronic acids or esters with sterically hindered haloarenes in thepresence of palladium (II) catalysts. This reaction has become known asthe Suzuki reaction.

B. E. Huff et al., Organic Synthesis, 75, 53 (1998) describe thesynthesis of unsymmetrical biaryls using a modified Suzukicross-coupling to form 4-biphenylcarbox-aldehyde.

J. P. Wolfe, et al., J. Am. Chem. Soc., 1999, 121, 9550 describe the useof highly active palladium catalysts for Suzuki coupling reactions.

WO 00/22037 describes the stabilization of solid, shaped and colored waxarticles using a malonate UV absorber which may be substituted by ahindered amine group.

Japanese Hei 5-93164 discloses the use of benzotriazole UV absorbers andhindered amines in stabilizing pigmented wax crayons.

Copending U.S. patent application Ser. Nos. 09/496,084; 09/495,495 and09/495,496 all describe the stabilization of candle wax using othertypes of benzotriazole UV absorbers.

DETAILED DESCRIPTION

The instant invention pertains to compounds of formula I or II

wherein

-   -   R is phenyl, naphthyl, biphenylyl, 9-phenanthryl or said phenyl,        naphthyl, biphenylyl or 9-phenanthryl substituted by one to        three alkyl of 1 to 18 carbon atoms, phenylalkyl of 7 to 15        carbon atoms, R₃S—, R₃SO—, R₃SO₂, aryl of 6 to 10 carbon atoms,        perfluoroalkyl of 1 to 12 carbon atoms, halogen, nitro, cyano,        carboxyl, alkoxycarbonyl of 2 to 19 carbon atoms, hydroxyl,        alkoxy of 1 to 18 carbon atoms, aryloxy of 6 to 10 carbon atoms,        aralkoxy of 7 to 15 carbon atoms, vinyl, acetyl, acetamido,        amino, dialkylamino of 2 to 12 carbon atoms, formyl, thioalkoxy        of 1 to 18 carbon atoms, hydroxymethyl, amino-methyl,        halomethyl, sulfato, phosphato or where any two substituents        form a benzo ring with the aryl moiety to which they are        attached,

T is a direct bond, 1,4-phenylene or said phenylene substituted by oneor two alkyl of 1 to 12 carbon atoms,

R₃ is alkyl of 1 to 18 carbon atoms, phenylalkyl of 7 to 15 carbon atomsor aryl of 6 to 10 carbon atoms,

E₁ is hydrogen, straight or branched alkyl of 1 to 24 carbon atoms,phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or saidphenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4carbon atoms,

E₂ is straight or branched alkyl chain of 1 to 24 carbon atoms, straightor branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or saidphenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3alkyl of 1 to 4 carbon atoms; or E₂ is alkyl of 1 to 24 carbon atoms oralkenyl of 2 to 18 carbon atoms substituted by one or more —OH, —OCOE₃,—NH₂, —NHCOE₃ or —COOE₃, or mixtures thereof; or said alkyl or saidalkenyl interrupted by one or more —O— which can be unsubstituted orsubstituted by one or more —OH groups; where E₃ is hydrogen or alkyl of1 to 24 carbon atoms, and where said alkyl is interrupted by one or more—O— and which can be substituted by one or more —OH or —OR₂₁ groupswhere R₂₁ is alkyl of 1 to 12 carbon atoms;

and

with the proviso that5-phenyl-2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole isexcluded; and

with the further proviso that, when E₁ is hydrogen, methyl or ethyl andE₂ is methyl or ethyl, R is not phenyl.

Another embodiment are the compounds of formula I are those where R isphenyl, 2-naphthyl, 3-biphenylyl, 4-biphenylyl, 9-phenanthryl,2-trifluoromethylphenyl, 3-trifluoromethylphenyl,4-trifluoromethylphenyl, 3,5-ditrifluoromethylphenyl, 4-cyanophenyl,3-methylphenyl, 3-isopropylphenyl, 3-fluorophenyl, 3-chlorophenyl,3-bromophenyl, 3-iodophenyl, 3-methoxyphenyl, 3-ethoxyphenyl,3-benzyloxyphenyl, 3-hydroxyphenyl, 3-hydroxymethylphenyl,3-thiomethylphenyl, 3-bromomethylphenyl, 3-cyanophenyl, 3-vinylphenyl,3-acetylphenyl, 3-aminophenyl, 3-acetamidophenyl, 3-formylphenyl,3-isothiocyano-phenyl, 2-ethylphenyl, 2-cyanophenyl, 2-acetylphenyl,2-bromomethylphenyl, 2-bromophenyl, 2-vinylphenyl, 2-aminophenyl,2-hydroxyphenyl, 2-ethoxyphenyl, 2-fluorophenyl, 2-chlorophenyl,2-methoxyphenyl, 2-formylphenyl, 2-methylphenyl, 4-n-butylphenyl,4-n-nonylphenyl, 4-methoxycarbonylphenyl, 4-cyanomethylphenyl,4-aminomethylphenyl, 4-isobutylphenyl, 4-iodophenyl, 4-thioethylphenyl,4-bromomethylphenyl, 4-benzyloxyphenyl, 4-acetylphenyl,4-dimethylaminophenyl, 4-hydroxyphenyl, 4-isopropylphenyl,4-tert-butylphenyl, 4-aminophenyl, 4-n-amylphenyl, 4-ethylphenyl,4-hydroxymethylphenyl, 4-ethoxyphenyl, 4-vinylphenyl, 4-formylphenyl,4-carboxyphenyl, 4-thiomethylphenyl, 4-phenoxyphenyl, 4-methoxyphenyl,4-methylphenyl, 4-chlorophenyl, 4-fluorophenyl, 4-bromophenyl,2,6-dimethylphenyl, 3,5-dichlorophenyl, 3,5-dimethylphenyl,3,5-dibromophenyl, 3,5-difluorophenyl, 3-chloro-4-fluorophenyl,3,4-difluorophenyl, 3-amino-4-methylphenyl, 3,4-dichlorophenyl,3-hydroxy-4-methylphenyl, 3-amino-4-methylphenyl, 3-fluoro-4-bromophenylor 3-fluoro-4-formylphenyl, and where E₁ and E₂ are independentlystraight or branched chain alkyl of 4 to 24 carbon atoms or phenylalkylof 7 to 15 carbon atoms, or E₁ is additionally phenyl.

Another embodiment of the instant invention are compounds of formula IIwhere T is a direct bond, 1,4-phenylene or 2,5-di-n-hexyl-1,4-phenyeneand where E₁ and E₂ are independently a straight or branched chain alkylof 4 to 24 carbon atoms or phenylalkyl of 7 to 15 carbon atoms.

Another embodiment of the instant invention are the compounds of formulaI or II where R is phenyl, 2-trifluoromethylphenyl,3-trifluoromethylphenyl, 4-trifluoromethylphenyl,3,5-di-trifluoromethylphenyl, 4-cyanophenyl, 4-methoxyphenyl or1,1′biphenyl-4-ylphenyl, T is 1,4-phenylene, E₁ is phenyl or α-cumyl,and E₂ is tert-butyl or tert-octyl.

Still another embodiment of the instant invention are compounds offormula I where R is phenyl or 4-trifluoromethylphenyl; E₁ is α-cumyl;and E₂ is tert-octyl.

The instant invention also pertains to the method of making the instantcompounds of formula I or II

where R, T, E₁ and E₂ are as defined above,

by the reaction of an arylboronic acid or ester of formula III or IVR—B(OR₁)(OR₂)  (III)(R₂O)(R₁O)B-T-B(OR₁)(OR₂)  (IV)where R₁ and R₂ are independently hydrogen, alkyl of 1 to 12 carbonatoms, or R₁ and R₂ together are alkylene of 2 to 4 carbon atoms;

with a 5-substituted benzotriazole of formula V

where X is chloro, bromo or iodo, or tosylate,

in the presence of an effective amount of a palladium (II) catalyst. andoptionally in the additional presence of a ligand, such astriphenylphosphine, at a temperature between 10 to 100° C., preferablybetween 50 to 95° C.

When a ligand is used, the ligand is triphenylphosphine,2-(di-tert-butyl-phosphino)biphenyl,1,1′-bis[2,4,8,10-tetrakis(tert-butyl)-dibenzo[d,f][1,3,2]dioxa-phosphepin-6-yl]ferrocene,tris(2,4-di-tert-butylphenyl) phosphite or2,2′,2″-nitrilo-[triethyl-tris(3,3′,5,5′-tetra-tert-butyl-1,1′biphenyl-2,2′-diyl)phosphite].In another embodiment, the ligand is triphenylphosphine.

Preferably the amount of palladium (II) catalyst is 0.01 to 10 molpercent.

In one embodiment of the invention, an anhydrous process is used withdioxane as solvent and potassium fluoride as a base; or the process canbe run using n-propanol or isopropanol as solvent with a small amount ofwater and aqueous sodium carbonate as a base.

When any of R₁ to R₃ or any of E₁ to E₃ is alkyl, such groups are,straight or branched chain, for example, methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl,n-octyl, 2-ethylhexyl, tert-octyl, lauryl, undecyl, tert-dodecyl,tridecyl, n-hexadecyl, n-octadecyl and eicosyl; when any of saidradicals is alkenyl, such groups are, for example, allyl, methallyl.2-n-hexenyl, 4-n-octenyl or oleyl; when any of said radicals iscycloalkyl, such groups are, for example, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl or cyclododecyl; when any of said radicals arephenylalkyl, such groups are, for example, benzyl, α-phenethyl,2-phenethyl, α-methylbenzyl or α,α-dimethylbenzyl; and when any of saidradicals is aryl, they are, for example, phenyl, α-naphthyl orβ-naphthyl or when substituted by alkyl are, for example, tolyl andxylyl. When alkyl is substituted by one or more —O— groups and/orsubstituted by one or more —OH, these groups can be hydroxymethyl,2-hydroxyethyl or 2-hydroxypropyl or can be, for example,—(OCH₂CH₂)_(w)OH or —(OCH₂CH₂)_(w)OR₂₁ where w is 1 to 12 and R₂₁ isalkyl of 1 to 12 carbon atoms; when any of said radicals is halogen,they are, for example, fluoro, chloro, bromo or iodo; when any of saidradicals is alkoxycarbonyl, they are, for example, methoxycarbonyl,ethoxycarbonyl, butoxycarbonyl, hexyloxycarbonyl, octyloxycarbonyl, ordodecyloxycarbonyl; when any of said radicals is alkoxy or aryloxy, theyare, for example, the same alkyl or same aryl definition as seen above.

The instant invention also pertains to a composition stabilized againstthermal, oxidative or light-induced degradation which comprises,

(a) an organic material subject to thermal, oxidative or light-induceddegradation, and

(b) an effective stabilizing amount of a compound of formula I or II

wherein

R is phenyl, naphthyl, biphenylyl, 9-phenanthryl or said phenyl,naphthyl, biphenylyl or 9-phenanthryl substituted by one to three alkylof 1 to 18 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, R₃S—,R₃SO—, R₃SO₂, aryl of 6 to 10 carbon atoms, perfluoroalkyl of 1 to 12carbon atoms, halogen, nitro, cyano, carboxyl, alkoxycarbonyl of 2 to 19carbon atoms, hydroxyl, alkoxy of 1 to 18 carbon atoms, aryloxy of 6 to10 carbon atoms, aralkoxy of 7 to 15 carbon atoms, vinyl, acetyl,acetamido, amino, dialkylamino of 2 to 12 carbon atoms, formyl,thioalkoxy of 1 to 18 carbon atoms, hydroxymethyl, amino-methyl,halomethyl, sulfato, phosphato or where any two substituents form abenzo ring with the aryl moiety to which they are attached,

T is a direct bond, 1,4-phenylene or said phenylene substituted by oneor two alkyl of 1 to 12 carbon atoms,

R₃ is alkyl of 1 to 18 carbon atoms, phenylalkyl of 7 to 15 carbon atomsor aryl of 6 to 10 carbon atoms,

E₁ is hydrogen, straight or branched alkyl of 1 to 24 carbon atoms,phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or saidphenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4carbon atoms,

E₂ is straight or branched alkyl chain of 1 to 24 carbon atoms, straightor branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or saidphenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3alkyl of 1 to 4 carbon atoms; or E₂ is alkyl of 1 to 24 carbon atoms oralkenyl of 2 to 18 carbon atoms substituted by one or more —OH, —OCOE₃,—NH₂, —NHCOE₃ or —COOE₃, or mixtures thereof; or said alkyl or saidalkenyl interrupted by one or more —O— which can be unsubstituted orsubstituted by one or more —OH groups; where E₃ is hydrogen or alkyl of1 to 24 carbon atoms, and where said alkyl is interrupted by one or more—O— and which can be substituted by one or more —OH or -0R₂₁ groupswhere R₂₁ is alkyl of 1 to 12 carbon atoms.

The organic material is a natural, semi-synthetic or synthetic polymer,such as a thermoplastic polymer.

In other embodiments, the polymer is a polyolefin or polycarbonate, suchas polyethylene or polypropylene; or polypropylene; or the polymer is astyrenic, ABS, a nylon, a polyester such as poly(ethylene terephthalate)or poly(butylene terephthalate), a polyurethane, an acrylate, a rubbermodified styrenic, poly(vinyl chloride), poly(vinyl butyral), polyacetal(polyoxymethylene), poly(ethylene naphthalenedicarboxylate), or otherblends or copolymers such as poly(ethylene/1,4-cyclohexylenedimethyleneterephthalate) PETG or an ionomer.

In another embodiment of the instant invention, the organic material isa resin selected from the group consisting of a thermoset acrylicmelamine resin, an acrylic urethane resin, an epoxy carboxy resin, asilane modified acrylic melamine, an acrylic resin with carbamatependant groups crosslinked with melamine or an acrylic polyol resincrosslinked with melamine containing carbamate groups.

In still other embodiments, the resin is a thermoset acrylic melamineresin or an acrylic urethane resin.

In yet another embodiment of the instant invention, the organic materialis a recording material.

The recording materials according to the invention are suitable forpressure-sensitive copying systems, photocopying systems usingmicrocapsules, heat-sensitive copying systems, photographic materialsand ink jet printing.

The recording materials according to the invention are distinguished byan unexpected improvement in quality, especially with regard to thefastness to light.

The recording materials according to the invention have the constructionknown for the particular use. They consist of a customary carrier, forexample, paper or plastic film, which has been coated with one or morelayers. Depending on the type of material, these layers contain theappropriate necessary components, in the case of photographic materials,for example, silver halide emulsions, dye couplers, dyes and the like.Material particularly suitable for ink jet printing has a layerparticularly absorptive for ink on a customary carrier. Uncoated papercan also be employed for ink jet printing. In this case the paper actsat the same time as the carrier material and as the ink-absorbent layer.Suitable material for ink jet printing is, for example, described inU.S. Pat. No. 5,073,448 which is incorporated herein by reference.

The recording material can also be transparent as, for example, in thecase of projection films.

The compounds of formula I or II can be incorporated into the cardermaterial as early as the production of the latter, in the production ofpaper, for example, being added to the paper pulp. A second method ofapplication is to spray the carder material with an aqueous solution ofcompounds of formula I or II or to add the compounds to the coatingcomposition.

Coating compositions intended for transparent recording materialssuitable for projection cannot contain any particles which scatterlight, such as pigments and fillers.

The dye-binding coating composition can contain a number of otheradditives, for example, antioxidants, light stabilizers (including alsoUV absorbers which do not fall under the scope of the UV absorbers ofthis invention), viscosity improvers, fluorescent brighteners, biocidesand/or antistatic agents.

The coating composition is usually prepared as follows: thewater-soluble components, for example, the binder, are dissolved inwater and stirred together; the solid components, for example, fillersand other additives already described, are dispersed in this aqueousmedium; and disperison is advantageously carried out by means ofdevices, for example, ultrasonic systems, turbine stirrers,homogenizers, colloid mills, bead mills, sand mills, high-speed stirrersand the like. The compounds of formula I or II can be easilyincorporated into the coating composition.

The recording material according to this invention preferably contains 1to 5000 mg/m², in particular 50–1200 mg/m², of a compound of formula Ior II.

As already mentioned, the recording materials according to the inventionembrace a wide field. The compounds of formula I or II can, for example,be employed in pressure-sensitive copying systems. They can beintroduced either into the paper in order to protect themicroencapsulated dye precursors there from light, or into the binder ofthe developer layer in order to protect the dyes formed there.

Photocopying systems using light-sensitive microcapsules which aredeveloped by means of pressure are described in U.S. Pat. Nos.4,416,966; 4,483,912; 4,352,200; 4,535,050; 4,535,463; 4,551,407;4,562,137 and 4,608,330; and also in EP-A 139,479; EP-A 162,664; EP-A164,931; EP-A 237,024; EP-A 237,025 and EP-A 260,129. In all thesesystems, the compounds can be put into the dye-receiving layer. Thecompounds can, however, also be put into the donor layer in order toprotect the color formers from light.

Photographic materials which can be stabilized are photographic dyes andlayers containing such dyes or precursors thereof, for example,photographic paper and films. Suitable materials are, for example,described in U.S. Pat. No. 5,364,749 which is incorporated herein byreference. The compounds of formula I or II act here as a UV filteragainst electrostatic flashes. In color photographic materials, couplersand dyes are also protected against photochemical decomposition.

The instant compounds can be used for all types of color photographicmaterials. For example, they can be employed for color paper, colorreversal paper, direct-positive color material, color negative film,color positive film, color reversal film and the like. They arepreferably used inter alia for photographic color material whichcontains a reversal substrate or form positives.

Color-photographic recording materials usually contain, on a support, ablue-sensitive and/or a green-sensitive and/or a red-sensitive silverhalide emulsion layer and, if desired, a protection layer, with theinstant compounds being, preferably, either in the green-sensitive orthe red-sensitive layer or in a layer between the green-sensitive andthe red-sensitive layer or in a layer on top of the silver halideemulsion layers.

The compounds of formula I or II can also be employed in recordingmaterials based on the principles of photopolymerization,photoplasticization or the rupture of microcapsules, or in cases whereheat-sensitive and light-sensitive diazonium salts, leuko dyes having anoxidizing agent or dye lactones having Lewis acids are used.

Furthermore, the instant compounds can be employed in recordingmaterials for dye diffusion transfer printing, thermal wax transferprinting and non-matrix printing and for use with electrostatic,electrographic, electrophoretic, magnetographic andlaser-electrophotographic printers and pen-plotters. Of the above,recording materials for dye diffusion transfer printing are preferred,for example, as described in EP-A 507,734.

The instant compounds can also be employed in inks, such as for ink jetprinting, for example, as described in U.S. Pat. No. 5,098,477 which isincorporated herein by reference.

The instant compounds also are effective in the protection of dyespresent in candle wax from premature degradation and fading.

The instant compounds of formula I or II are also useful in adhesivesused in solar films, optical films and other laminated structuresagainst the adverse effects of ultraviolet light and actinic radiation.

The compounds of this invention exhibit superior hydrolytic stability,handling and storage stability as well as good resistance toextractability when present in a stabilized composition.

The methodology to make the instant compounds is described in the priorart. The intermediates needed to make the instant compounds are largelyitems of commerce.

In general polymers which can be stabilized include

-   1. Polymers of monoolefins and diolefins, for example polypropylene,    polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,    polyisoprene or polybutadiene, as well as polymers of cycloolefins,    for instance of cyclopentene or norbornene, polyethylene (which    optionally can be crosslinked), for example high density    polyethylene (HDPE), low density polyethylene (LDPE), linear low    density polyethylene (LLDPE), branched low density polyethylene    (BLDPE). Polyolefins, i.e. the polymers of monoolefins exemplified    in the preceding paragraph, preferably polyethylene and    polypropylene, can be prepared by different, and especially by the    following, methods:    -   a) radical polymerisation (normally under high pressure and at        elevated temperature).    -   b) catalytic polymerisation using a catalyst that normally        contains one or more than one metal of groups IVb, Vb, VIb or        VIII of the Periodic Table. These metals usually have one or        more than one ligand, typically oxides, halides, alcoholates,        esters, ethers, amines, alkyls, alkenyls and/or aryls that may        be either π- or σ-coordinated. These metal complexes may be in        the free form or fixed on substrates, typically on activated        magnesium chloride, titanium(III) chloride, alumina or silicon        oxide. These catalysts may be soluble or insoluble in the        polymerisation medium. The catalysts can be used by themselves        in the polymerisation or further activators may be used,        typically metal alkyls, metal hydrides, metal alkyl halides,        metal alkyl oxides or metal alkyloxanes, said metals being        elements of groups Ia, IIa and/or IIIa of the Periodic Table.        The activators may be modified conveniently with further ester,        ether, amine or silyl ether groups. These catalyst systems are        usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta),        TNZ (DuPont), metallocene or single site catalysts (SSC).-   2. Mixtures of the polymers mentioned under 1), for example mixtures    of polypropylene with polyisobutylene, polypropylene with    polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of    different types of polyethylene (for example LDPE/HDPE).-   3. Copolymers of monoolefins and diolefins with each other or with    other vinyl monomers, for example ethylene/propylene copolymers,    linear low density polyethylene (LLDPE) and mixtures thereof with    low density polyethylene (LDPE), propylene/but-1-ene copolymers,    propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,    ethylene/hexene copolymers, ethylene/methylpentene copolymers,    ethylene/heptene copolymers, ethylene/octene copolymers,    propylene/butadiene copolymers, isobutylene/isoprene copolymers,    ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate    copolymers, ethylene/vinyl acetate copolymers and their copolymers    with carbon monoxide or ethylene/acrylic acid copolymers and their    salts (ionomers) as well as terpolymers of ethylene with propylene    and a diene such as hexadiene, dicyclopentadiene or    ethylidene-norbornene; and mixtures of such copolymers with one    another and with polymers mentioned in 1) above, for example    polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl    acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers    (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random    polyalkylene/carbon monoxide copolymers and mixtures thereof with    other polymers, for example polyamides.-   4. Hydrocarbon resins (for example C₅–C₉) including hydrogenated    modifications thereof (e.g. tackifiers) and mixtures of    polyalkylenes and starch.-   5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).-   6. Copolymers of styrene or α-methylstyrene with dienes or acrylic    derivatives, for example styrene/butadiene, styrene/acrylonitrile,    styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate,    styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride,    styrene/acrylonitrile/methyl acrylate; mixtures of high impact    strength of styrene copolymers and another polymer, for example a    polyacrylate, a diene polymer or an ethylene/propylene/diene    terpolymer, and block copolymers of styrene such as    styrene/butadiene/styrene, styrene/isoprene/styrene,    styrene/ethylene/butylene/styrene or    styrene/ethylene/propylene/styrene.-   7. Graft copolymers of styrene or α-methylstyrene, for example    styrene on polybutadiene, styrene on polybutadiene-styrene or    polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile    (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and    methyl methacrylate on polybutadiene; styrene and maleic anhydride    on polybutadiene; styrene, acrylonitrile and maleic anhydride or    maleimide on polybutadiene; styrene and maleimide on polybutadiene;    styrene and alkyl acrylates or methacrylates on polybutadiene;    styrene and acrylonitrile on ethylene/propylene/diene terpolymers;    styrene and acrylonitrile on polyalkyl acrylates or polyalkyl    methacrylates, styrene and acrylonitrile on acrylate/butadiene    copolymers, as well as mixtures thereof with the copolymers listed    under 6), for example the copolymer mixtures known as ABS, MBS, ASA    or AES polymers.-   8. Halogen-containing polymers such as polychloroprene, chlorinated    rubbers, chlorinated PVC, chlorinated or sulfochlorinated    polyethylene, copolymers of ethylene and chlorinated ethylene,    epichlorohydrin homo- and copolymers, especially polymers of    halogen-containing vinyl compounds, for example polyvinyl chloride,    polyvinylidene chloride, polyvinyl fluoride, polyvinylidene    fluoride, as well as copolymers thereof such as vinyl    chloride/vinylidene chloride, vinyl chloride/vinyl acetate or    vinylidene chloride/vinyl acetate copolymers.-   9. Polymers derived from α,β-unsaturated acids and derivatives    thereof such as polyacrylates and polymethacrylates; polymethyl    methacrylates, polyacrylamides and polyacrylonitriles,    impact-modified with butyl acrylate.-   10. Copolymers of the monomers mentioned under 9) with each other or    with other unsaturated monomers, for example acrylonitrile/butadiene    copolymers, acrylonitrile/alkyl acrylate copolymers,    acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide    copolymers or acrylonitrile/alkyl methacrylate/butadiene    terpolymers.-   11. Polymers derived from unsaturated alcohols and amines or the    acyl derivatives or acetals thereof, for example polyvinyl alcohol,    polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl    maleate, polyvinyl butyral, polyallyl phthalate or polyallyl    melamine; as well as their copolymers with olefins mentioned in 1)    above.-   12. Homopolymers and copolymers of cyclic ethers such as    polyalkylene glycols, polyethylene oxide, polypropylene oxide or    copolymers thereof with bisglycidyl ethers.-   13. Polyacetals such as polyoxymethylene and those polyoxymethylenes    which contain ethylene oxide as a comonomer, polyacetals modified    with thermoplastic polyurethanes, acrylates or MBS.-   14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene    oxides with styrene polymers or polyamides.-   15. Polyurethanes derived from hydroxyl-terminated polyethers,    polyesters or polybutadienes on the one hand and aliphatic or    aromatic polyisocyanates on the other, as well as precursors    thereof.-   16. Polyamides and copolyamides derived from diamines and    dicarboxylic acids and/or from aminocarboxylic acids or the    corresponding lactams, for example polyamide 4, polyamide 6,    polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide    12, aromatic polyamides starting from m-xylene diamine and adipic    acid; polyamides prepared from hexamethylenediamine and isophthalic    or/and terephthalic acid and with or, without an elastomer as    modifier, for example poly-2,4,4,-trimethylhexamethylene    terephthalamide or poly-m-phenylene isophthalamide; and also block    copolymers of the aforementioned polyamides with polyolefins, olefin    copolymers, ionomers or chemically bonded or grafted elastomers; or    with polyethers, e.g. with polyethylene glycol, polypropylene glycol    or polytetramethylene glycol; as well as polyamides or copolyamides    modified with EPDM or ABS; and polyamides condensed during    processing (RIM polyamide systems).-   17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.-   18. Polyesters derived from dicarboxylic acids and diols and/or from    hydroxycarboxylic acids or the corresponding lactones, for example    polyethylene terephthalate, polybutylene terephthalate,    poly-1,4-dimethylolcyclohexane terephthalate and    polyhydroxybenzoates, as well as block copolyether esters derived    from hydroxyl-terminated polyethers; and also polyesters modified    with polycarbonates or MBS.-   19. Polycarbonates and polyester carbonates.-   20. Polysulfones, polyether sulfones and polyether ketones.-   21. Crosslinked polymers derived from aldehydes on the one hand and    phenols, ureas and melamines on the other hand, such as    phenolformaldehyde resins, urea/formaldehyde resins and    melamine/formaldehyde resins.-   22. Drying and non-drying alkyd resins.-   23. Unsaturated polyester resins derived from copolyesters of    saturated and unsaturated dicarboxylic acids with polyhydric    alcohols and vinyl compounds as crosslinking agents, and also    halogen-containing modifications thereof of low flammability.-   24. Crosslinkable acrylic resins derived from substituted acrylates,    for example epoxy acrylates, urethane acrylates or polyester    acrylates.-   25. Alkyd resins, polyester resins and acrylate resins crosslinked    with melamine resins, urea resins, polyisocyanates or epoxy resins.-   26. Crosslinked epoxy resins derived from polyepoxides, for example    from bisglycidyl ethers or from cycloaliphatic diepoxides.-   27. Natural polymers such as cellulose, rubber, gelatin and    chemically modified homologous derivatives thereof, for example    cellulose acetates, cellulose propionates and cellulose butyrates,    or the cellulose ethers such as methyl cellulose; as well as rosins    and their derivatives.-   28. Blends of the aforementioned polymers (polyblends), for example    PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,    PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic    PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA    6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO.-   29. Naturally occurring and synthetic organic materials which are    pure monomeric compounds or mixtures of such compounds, for example    mineral oils, animal and vegetable fats, oil and waxes, or oils,    fats and waxes based on synthetic esters (e.g. phthalates, adipates,    phosphates or trimellitates) and also mixtures of synthetic esters    with mineral oils in any weight ratios, typically those used as    spinning compositions, as well as aqueous emulsions of such    materials.-   30. Aqueous emulsions of natural or synthetic rubber, e.g. natural    latex or latices of carboxylated styrene/butadiene copolymers.-   31. Polysiloxanes such as the soft, hydrophilic polysiloxanes    described, for example, in U.S. Pat. No. 4,259,467; and the hard    polyorganosiloxanes described, for example, in U.S. Pat. No.    4,355,147.-   32. Polyketimines in combination with unsaturated acrylic    polyacetoacetate resins or with unsaturated acrylic resins. The    unsaturated acrylic resins include the urethane acrylates, polyether    acrylates, vinyl or acryl copolymers with pendant unsaturated groups    and the acrylated melamines. The polyketimines are prepared from    polyamines and ketones in the presence of an acid catalyst.-   33. Radiation curable compositions containing ethylenically    unsaturated monomers or oligomers and a polyunsaturated aliphatic    oligomer.-   34. Epoxymelamine resins such as light-stable epoxy resins    crosslinked by an epoxy functional coetherified high solids melamine    resin such as LSE-4103 (Monsanto).

In general, the compounds of the present invention are employed in fromabout 0.01 to about 5% by weight of the stabilized composition, althoughthis will vary with the particular substrate and application. Anadvantageous range is from about 0.05 to about 3%, and especially 0.05to about 1%. However, some high performance films or in UV absorbinglayers of laminates such as those produced by coextrusion may containfrom 5–15% by weight of the instant compounds. Concentrations of 5–10%by weight are typical in certain coextrusion applications.

The stabilizers of the instant invention may readily be incorporatedinto the organic polymers by conventional techniques, at any convenientstage prior to the manufacture of shaped articles therefrom. Forexample, the stabilizer may be mixed with the polymer in dry powderform, or a suspension or emulsion of the stabilizer may be mixed with asolution, suspension, or emulsion of the polymer. The resultingstabilized polymer compositions of the invention may optionally alsocontain from about 0.01 to about 5%, preferably from about 0.025 toabout 2%, and especially from about 0.1 to about 1% by weight of variousconventional additives, such as the materials listed below, or mixturesthereof.

-   1. Antioxidants-   1.1. Alkylated monophenols, for example,-   2,6-di-tert-butyl-4-methylphenol-   2-tert-butyl-4,6-dimethylphenol-   2,6-di-tert-butyl-4-ethylphenol-   2,6-di-tert-butyl-4-n-butylphenol-   2,6-di-tert-butyl-4-1-butylphenol-   2,6-di-cyclopentyl-4-methylphenol-   2-(α-methylcyclohexyl)-4,6-dimethylphenol-   2,6-di-octadecyl-4-methylphenol-   2,4,6-tri-cyclohexylphenol-   2,6-di-tert-butyl-4-methoxymethylphenol-   1.2. Alkylated hydroguinones, for example,-   2,6-di-tert-butyl-4-methoxyphenol-   2,5-di-tert-butyl-hydroquinone-   2,5-di-tert-amyl-hydroquinone-   2,6-diphenyl-4-octadecyloxyphenol-   1.3. Hydroxylated thiodiphenyl ethers, for example,-   2,2′-thio-bis-(6-tert-butyl-4-methylphenol)-   2,2′-thio-bis-(4-octylphenol)-   4,4′-thio-bis-(6-tert-butyl-3-methylphenol)-   4,4′-thio-bis-(6-tert-butyl-2-methylphenol)-   1.4. Alkylidene-bisphenols, for example,-   2,2′-methylene-bis-(6-tert-butyl-4-methylphenol)-   2,2′-methylene-bis-(6-tert-butyl-4-ethylphenol)-   2,2′-methylene-bis-[4-methyl-6-(α-methylcyclohexyl)-phenol]-   2,2′-methylene-bis-(4-methyl-6-cyclohexylphenol)-   2,2′-methylene-bis-(6-nonyl-4-methylphenol)-   2,2′-methylene-bis-[6-(α-methylbenzyl)-4-nonylphenol]-   2,2′-methylene-bis-[6-(α,α-dimethylbenzyl)-4-nonylphenol]-   2,2′-methylene-bis-(4,6-di-tert-butylphenol)-   2,2′-ethylidene-bis-(4,6-di-tert-butylphenol)-   2,2′-ethylidene-bis-(6-tert-butyl-4-isobutylphenol)-   4,4′-methylene-bis-(2,6-di-tert-butylphenol)-   4,4′-methylene-bis-(6-tert-butyl-2-methylphenol)-   1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane-   2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol-   1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane-   1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane-   ethyleneglycol    bis-[3,3-bis-(3′-tert-butyl-4′-hydroxyphenyl)-butyrate]-   di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene-   di-[2-(3′-tert-butyl-2′-hydroxy-5′-methyl-benzyl)-6-tert-butyl-4-methylphenyl]    terephthalate.-   1.5. Benzyl compounds for example,-   1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene-   di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide-   3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl    ester-   bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate-   1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate-   1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate-   3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester-   3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester,    calcium-salt-   1.6. Acylaminophenols, for example,-   4-hydroxy-lauric acid anilide-   4-hydroxy-stearic acid anilide-   2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine-   octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate-   1.7. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid    with monohydric or polyhydric alcohols, for example,

methanol diethylene glycol octadecanol triethylene glycol 1,6-hexanediolpentaerythritol neopentyl glycol tris-hydroxyethyl isocyanuratethiodiethylene glycol di-hydroxyethyl oxalic acid diamidetriethanolamine triisopropanolamine

-   1.8. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic    acid with monohydric or polyhydric alcohols, for example,

methanol diethylene glycol octadecanol triethylene glycol 1,6-hexanediolpentaerythritol neopentyl glycol tris-hydroxyethyl isocyanuratethiodiethylene glycol di-hydroxyethyl oxalic acid diamidetriethanolamine triisopropanolamine

-   1.9. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid    for example,-   N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine-   N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine-   N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine-   1.10 Diarylamines, for example,-   diphenylamine, N-phenyl-1-naphthylamine,    N-(4-tert-octylphenyl)-1-naphthylamine,-   4,4′-di-tert-octyl-diphenylamine, reaction product of    N-phenylbenzylamine and-   2,4,4-trimethylpentene, reaction product of diphenylamine and    2,4,4-trimethylpentene, reaction product of N-phenyl-1-naphthylamine    and 2,4,4-trimethylpentene.-   2. UV absorbers and light stabilizers-   2.1. 2-(2′-Hydroxyphenyl)-benzotriazoles, for example, the    5′-methyl-, 3′,5′-di-tert-butyl-, 5′-tert-butyl-,    5′-(1,1,3,3-tetramethylbutyl)-, 5-chloro-3′,5′-di-tert-butyl-,    5-chloro-3′-tert-butyl-5′-methyl-, 3′-sec-butyl-5′-tert-butyl-,    4′-octoxy, 3′,5′-di-tert-amyl-, 3′,5′-bis-(α,α-dimethylbenzyl),    3′-tert-butyl-5′-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,    3′-dodecyl-5′-methyl-, and    3′-tert-butyl-5′-(2-octyloxycarbonyl)ethyl-, and    dodecylated-5′-methyl derivatives.-   2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-,    4-methoxy-, 4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy,    4,2′,4′-trihydroxy- and 2′-hydroxy-4,4′-dimethoxy Derivatives.-   2.3. Esters of optionally substituted benzoic acids for example,    phenyl salicylate, 4-tert-butylphenyl salicylate, octylphenyl    salicylate, dibenzoylresorcinol,    bis-(4-tert-butylbenzoyl)-resorcinol, benzoylresorcinol,    3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl    ester and 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester.-   2.4. Acrylates, for example, α-cyano-β,β-diphenylacrylic acid ethyl    ester or isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester,    α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butyl    ester, β-carbomethoxy-p-methoxy-cinnamic acid methyl ester,    N-(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline.-   2.5. Nickel compounds, for example, nickel complexes of    2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1    or 1:2 complex, optionally with additional ligands such as    n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel    dibutyldithiocarbamate, nickel salts of    4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters,    such as of the methyl, ethyl or butyl ester, nickel complexes of    ketoximes such as of 2-hydroxy-4-methyl-phenyl undecyl ketoxime,    nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole,    optionally with additional ligands.-   2.6. Sterically hindered amines, for example    bis-(2,2,6,6-tetramethylpiperidyl) sebacate,    bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate,    n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acid    bis-(1,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of    1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic    acid, condensation product of    N,N′-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and    4-tert-octylamino-2,6-dichloro-s-triazine,    tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate,    tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)    1,2,3,4-butanetetracarboxylate,    1,1′(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone),    bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,    1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine.-   2.7. Oxalic acid diamides, for example, 4,4′-di-octyloxy-oxanilide,    2,2′-di-octyloxy-5,5′-di-tert-butyl-oxanilide,    2,2′-di-dodecyloxy-5,5′-di-tert-butyl-oxanilide,    2-ethoxy-2′-ethyl-oxanilide, N,N′-bis    (3-dimethylaminopropyl)-oxalamide,    2-ethoxy-5-tert-butyl-2′-ethyloxanilide and its mixture with    2-ethoxy-2′-ethyl-5,4′-di-tert-butyloxanilide and mixtures of ortho-    and para-methoxy- as well as of o- and p-ethoxy-disubstituted    oxanilides.-   2.8. Hydroxyphenyl-s-triazines, for example    2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine;    2,6-bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine;    2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine;    2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine;    2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine;    2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine;    2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,    2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine.-   3. Metal deactivators, for example, N,N′-diphenyloxalic acid    diamide, N-salicylal-N′-salicyloylhydrazine,    N,N′-bis-salicyloylhydrazine,    N,N′-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine,    3-salicyloylamino-1,2,4-triazole, bis-benzylidene-oxalic acid    dihydrazide.-   4. Phosphites and phosphonites, for example, triphenyl phosphite,    diphenylalkyl phosphites, phenyldialkyl phosphites,    tri-(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl    phosphite, di-stearyl-pentaerythritol diphosphite,    tris-(2,4-di-tert-butylphenyl) phosphite,    di-isodecyl-pentaerythritol diphosphite,    di-(2,4,6-tri-tert-butylphenyl)-pentaerythritol diphosphite,    di-(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite,    di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,    tristearyl-sorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl)    4,4′-diphenylylenediphosphonite.-   5. Compounds which destroy peroxide, for example, esters of    β-thiodipropionic acid, for example the lauryl, stearyl, myristyl or    tridecyl esters, mercapto-benzimidazole or the zinc salt of    2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyl    disulfide, pentaerythritol tetrakis-(β-dodecylmercapto)-propionate.-   6. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,    N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,    N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,    N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,    N-hexadecyl-N-octadecylhydroxylamine,    N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine    derived from hydrogenated tallow amine.-   7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone,    N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone,    N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone,    N-hexadecyl-alpha-pentadecyl nitrone,    N-octadecyl-alpha-heptadecyInitrone, N-hexadecyl-alpha-heptadecyl    nitrone, N-octadecyl-alpha-pentadecyl nitrone,    N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecyl    nitrone, nitrone derived from N,N-dialkylhydroxylamine derived from    hydrogenated tallow amine.-   8. Polyamide stabilizers, for example copper salts in combination    with iodides and/or phosphorus compounds and salts of divalent    manganese.-   9. Basic co-stabilizers, for example, melamine,    polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea    derivatives, hydrazine derivatives, amines, polyamides,    polyurethanes, alkali metal salts and alkaline earth metal salts of    higher fatty acids for example Ca stearate, Zn stearate, Mg    stearate, Na ricinoleate and K palmitate, antimony pyrocatecholate    or zinc pyrocatecholate.-   10. Nucleating agents, for example, 4-tert-butyl-benzoic acid,    adipic acid, diphenylacetic acid.-   11. Fillers and reinforcing agents, for example, calcium carbonate,    silicates, glass fibers, asbestos, talc, kaolin, mica, barium    sulfate, metal oxides and hydroxides, carbon black, graphite.-   12. Other additives, for example, plasticizers, lubricants,    emulsifiers, pigments, optical brighteners, flameproofing agents,    anti-static agents, blowing agents and thiosynergists such as    dilauryl thiodipropionate or distearyl thiodipropionate.-   13. Benzofuranones and indolinones, for example those disclosed in    U.S. Pat. Nos. 4,325,863, 4,338,244 or 5,175,312, or    3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,    5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,    3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],    5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,    3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,    3-(3,5-di-methyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

The co-stabilizers, with the exception of the benzofuranones listedunder 13, are added for example in concentrations of 0.01 to 10%,relative to the total weight of the material to be stabilized.

Further preferred compositions comprise, in addition to components (a)and (b) further additives, in particular phenolic antioxidants, lightstabilizers or processing stabilizers.

Particularly preferred additives are phenolic antioxidants (item 1 ofthe list), sterically hindered amines (item 2.6 of the list), phosphitesand phosphonites (item 4 of the list), UV absorbers (item 2 of the list)and peroxide-destroying compounds (item 5 of the list).

Additional additives (stabilizers) which are also particularly preferredare benzofuran-2-ones, such as described, for example, in U.S. Pat. Nos.4,325,863, 4,338,244 or 5,175,312.

The phenolic antioxidant of particular interest is selected from thegroup consisting of n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate), di-n-octadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)benzene,3,6-dioxaoctamethylenebis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate),2,6-di-tert-butyl-p-cresol,2,2′-ethylidene-bis(4,6-di-tert-butylphenol),1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocynurate,1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,1,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate,3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylenebis(3,5-1-tert-butyl-4-hydroxyhydrocinnamate),1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine,N,N′-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide),calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate),ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, andN,N′-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]-oxamide.

A most preferred phenolic antioxidant is neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate,1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,2,6-di-tert-butyl-p-cresol or2,2′-ethylidene-bis(4,6-di-tert-butylphenol).

The hindered amine compound of particular interest is selected from thegroup consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate,4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione,tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate,1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane,2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane, polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),polycondensation product of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, polycondensation product of4,4′-hexamethylenebis-(amino-2,2,6,6-tetramethylpiperidine) and1,2-dibromoethane, tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate,tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate, polycondensation product of2,4-dichloro-6-morpholino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N′,N″,N″′-tetrakis[(4,6-bis(butyl-1,2,2,6,6-pentamethylpiperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane,mixed[2,2,6,6-tetramethylpiperidin-4-yl/β,β,β′,β′-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl]1,2,3,4-butanetetracarboxylate, mixed[1,2,2,6,6-pentamethylpiperidin-4-yl/β,β,β′,β′-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl]1,2,3,4-butanetetracarboxylate,octamethylene bis(2,2,6,6-tetramethyl-piperidin-4-carboxylate),4,4′-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one),N-2,2,6,6-tetramethyl-piperidin-4-yl-n-dodecylsuccinimide,N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide,N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yln-dodecylsuccinimide,1-acetyl3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine,bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)]sebacate;a mixture ofbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]glutarateandbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]adipate;1-(2-hydroxy-2-methyl-propoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine;bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]adipate;bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-piperidin-4-yl]glutarate;bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]succinate;a mixture of bis1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]glutarateandbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]succinate;1-(4-octadecanoyloxy-2,2,6,6-tetramethylpiperidin-1-yloxy)-2-octadecanoyloxy-2-methylpropane;1-(2-hydroxy-2-methylpropoxy)-4-[9-(methoxy-carbonyl)nonanoyloxy]-2,2,6,6-tetramethylpiperidine;1-(2-hydroxy-2-methylpropoxy)-4-[5-(methoxy-carbonyl)pentanoyloxy]-2,2,6,6-tetramethylpiperidine;1-(2-hydroxy-2-methylpropoxy)-4-[3-(methoxy-carbonyl)propionyloxy]-2,2,6,6-tetramethylpiperidine;1-(2-hydroxy-2-methylpropoxy)-4-[4-(methoxy-carbonyl)-butyryloxy]-2,2,6,6-tetramethylpiperidine;condensation product of4-hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidinewith hexamethylene diisocyanate and terminated with methoxy;condensation product of4-hydroxy-1-(2-hydroxy-ethoxy)-2,2,6,6-tetramethylpiperidine withhexamethylene diisocyanate and terminated with methoxy; and thecondensation product of4-hydroxy-1-(2-hydroxy-1-phenethoxy)-2,2,6,6-tetramethylpiperidine withhexamethylene diisocyanate and terminated with methoxy.

A most preferred hindered amine compound isbis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, the polycondensationproduct of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidineand succinic acid, the polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N′,N″,N″′-tetrakis[(4,6-bis(butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino)-s-triazine-2-yl]-1,10-diamino-4,7-diazadecane.di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine,or1-(2-hydoxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine.

The instant composition can additionally contain another UV absorberselected from the group consisting of the benzotriazoles, thes-triazines, the oxanilides, the salicylates, the hydroxybenzophenones,the benzoates and the α-cyanoacrylates.

Particularly, the instant composition may additionally contain aneffective stabilizing amount of at least one other2-hydroxyphenyl-2H-benzotriazole; another tris-aryl-s-triazine; orhindered amine or mixtures thereof.

Preferably, the 2-hydroxyphenyl-2H-benzotriazole is selected from thegroup consisting of

-   2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;-   2-[2-hydroxy-3,5-di(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole;-   2-[2-hydroxy-3-(α,α-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole;-   2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]phenyl}-2H-benzotriazole;-   5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;-   5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole;-   2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole; and-   2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-benzotriazole.

Preferably, the other tris-aryl-s-triazine is selected from the groupconsisting of

-   2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine;-   2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine;-   2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)phenyl]-s-triazine;-   2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy*-2-hydroxypropyloxy)-5-α-cumylphenyl]-s-triazine.    (* denotes a mixture of octyloxy, nonyloxy and decyloxy groups.),    and-   2,4-bis(biphenylyl)-6-[2-hydroxy-4-(3-nonyloxy*-2-hydroxypropyloxy)phenyl]-s-triazine.    (* denotes a mixture of octyloxy, nonyloxy and decyloxy groups.)

The instant compounds are often used in conjunction with one or morecoadditive stabilizers where the coadditive stabilizer is a hinderedphenolic antioxidant selected from the group consisting ofneopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate,octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate,1,3,5-trimethyl-2,4,6-tris(3,5,-di-tert-butyl-4-hydroxybenzyl)benzene,1,2-bis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamoyl)hydrazine, calcium[bis(monoethyl 3,5-ditert-butyl-4-hydroxybenzyl)phosphonate],1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and1,3,5-tris(3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl) isocyanurate; oris an organophosphorus stabilizer selected from the group consisting oftris(2,4-di-tert-butylphenyl) phosphite,bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite,2,2′,2″-nitrilo[triethyl-tris-(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite], tetrakis(2,4-di-butylphenyl) 4,4′-biphenylenediphosphonite,tris(nonylphenyl) phosphite, bis(2,4-di-tert-butylphenyl)pentaerythrityl diphosphite, 2,2′-ethylidenebis(2,4-di-tert-butylphenyl)fluorophosphite and 2-butyl-2-ethylpropan-1,3-diyl2,4,6-tri-tert-butylphenyl phosphite; or is5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-2H-benzofuran-2-one; or isN,N-dialkylhydroxylamine made by the direct oxidation ofN,N-di(hydrogenated tallow)amine; or is a hindered amine selected fromthe group consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,the polycondensation product of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid,N,N′,N″,N″′-tetrakis[4,6-bis(butyl-1,2,2,6,6-pentamethylpiperidin-4-yl)amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane,the polycondensation product of4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and2,4-dichloro-6-tert-octylamino-s-triazine, the polycondensation productof 4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and2,4-dichloro-6-morpholino-s-triazine, the polycondensation product of4,4′-hexamethylenebis(amino-1,2,2,6,6-pentamethylpiperidine) and2,4-dichloro-6-morpholino-s-triazine, 2,2,6,6-tetramethylpiperidin-4-yloctadecanoate,3-dodecyl-1-(1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione,1,3,5-tris{N-cyclohexyl-N-[2-(2,2,6,6-tetramethylpiperazin-3-on-4-yl)ethyl]amino}-s-triazine,poly[methyl 3-(2,2,6,6-tetramethylpiperidin-4-yloxy)propyl]siloxane, thepolycondensation product of2,4-dichloro-6-(2,2,6,6-tetramethylpiperidin-4-yl)butylamino)-s-triazine,2,2′ethylene-bis{[2,4-(2,2,6,6-tetramethylpiperidin-4-yl)butylamino-s-triazin-6-yl]aminotrimethyleneamino},oligomer ofN-{[2-(N-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-4-yl}-N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamineterminated with 2,4-bis(dibutylamino)-s-triazin-6-yl,N,N′,N″-tris{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine,N,N′,N″′-tris{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamineandN,N′,N″,N′″-tetrakis{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine;or is another N-hydrocarbyloxy substituted hindered amines selected fromthe group consisting ofbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate,bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate,bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl octadecanoate,N,N′,N″-tris{2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine,N,N′,N″′-tris{2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamineandN,N′,N″,N′″-tetrakis{2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine;or a hydroxy substituted N-hydrocarbyloxy substituted hindered amineselected from the group consisting ofbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)]sebacate;a mixture ofbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]glutarateandbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]adipate;1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine;bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]adipate;bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]glutarate;bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]succinate;a mixture ofbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]glutarateandbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]succinate;1-(4-octadecanoyloxy-2,2,6,6-tetramethylpiperidin-1-yloxy)-2-octadecanoyloxy-2-methylpropane;1-(2-hydroxy-2-methylpropoxy)-4-[9-(methoxy-carbonyl)nonanoyloxy]-2,2,6,6-tetramethylpiperidine;1-(2-hydroxy-2-methylpropoxy)-4-[5-(methoxy-arbonyl)pentanoyloxy]-2,2,6,6-tetramethylpiperidine;1-(2-hydroxy-2-methylpropoxy)-4-[3-(methoxy-carbonyl)propionyloxy]-2,2,6,6-tetramethylpiperidine;1-(2-hydroxy-2-methylpropoxy)-4-[4-(methoxy-carbonyl)butyryloxy]-2,2,6,6-tetramethylpiperidine;or is a UV absorber selected from the group consisting of2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole,2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole,2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,2,4-di-tert-butylphenyl 3,5-di-tert-butyl4-hydroxybenzoate,2-hydroxy-4-n-octyloxybenzophenone,2,4-bis(2,4-dimethyphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine,oligomer ofN-{2-[(1-propoxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-4-yl}-N,N′-bis(1-propoxy-2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamineterminated with 2,4-bis(dibutylamino)-s-triazin-6-yl, the condensationproduct of 2-morpholino-4,6-dichloro-s-triazine withN,N′-bis(1,2,2,6,6-pentamethylpiperidin-4-yl)-1,6-hexanediamine; ormixtures thereof.

Preferably the coadditive stabilizer is neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate,tris(2,4-di-tert-butylphenyl) phosphite, N,N-dialkylhydroxylamine madeby the direct oxidation of N,N-di(hydrogenated tallow)amine,N,N′,N″,N″′-tetrakis[4,6-bis(butyl-1,2,2,6,6-pentamethylpiperidin-4-yl)amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane,the polycondensation product of4,4′-hexamethylene-bis(amino-2,2,6,6-tetramethylpiperidine) and2,4-dichloro-6-tert-octylamino-s-triazine, the polycondensation productof 4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and2,4-dichloro-6-morpholino-s-triazine, the polycondensation product of4,4′-hexamethylenebis(amino-1,2,2,6,6-pentamethylpiperidine) and2,4-dichloro-6-morpholino-s-triazine, oligomer ofN-{[2-(N-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-4-yl}-N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamineterminated with 2,4-bis(dibutylamino)-s-triazin-6-yl,N,N′,N″-tris{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine,N,N′,N″′-tris{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamineandN,N′,N″,N′″-tetrakis{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine,oligomer ofN-{2-[(1-propoxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-4-yl}-N,N′-bis(1-propoxy-2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamineterminated with 2,4-bis(dibutylamino)-s-triazin-6-yl, or thecondensation product of 2-morpholino-4,6-dichloro-s-triazine withN,N′-bis(1,2,2,6,6-pentamethylpiperidin-4-yl)-1,6-hexanediamine.

The alkyd resin lacquers which can be stabilized against the action oflight and moisture in accordance with the instant invention are theconventional stoving lacquers which are used in particular for coatingautomobiles (automobile finishing lacquers), for example lacquers basedon alkyd/melamine resins and alkyd/acrylic/melamine resins (see H.Wagner and H. F. Sarx, “Lackkunstharze” (1977), pages 99–123). Othercrosslinking agents include glycouril resins, blocked isocyanates orepoxy resins.

The lacquers stabilized in accordance with the invention are suitableboth for metal finish coatings and solid shade finishes, especially inthe case of retouching finishes, as well as various coil coatingapplications. The lacquers stabilized in accordance with the inventionare preferably applied in the conventional manner by two methods, eitherby the single-coat method or by the two-coat method. In the lattermethod, the pigment-containing base coat is applied first and then acovering coat of clear lacquer over it.

It is also to be noted that the compounds of the present invention areapplicable for use in non-acid catalyzed therm oset resins such asepoxy, epoxy-polyester, vinyl, alkyd, acrylic and polyester resins,optionally modified with silicon, isocyanates or isocyanurates. Theepoxy and epoxy-polyester resins are crosslinked with conventionalcross-linkers such as acids, acid anhydrides, amines and the like.Correspondingly, the epoxide may be utilized as the crosslinking agentfor various acrylic or polyester resin systems that have been modifiedby the presence of reactive groups on the backbone structure.

When used in two-coat finishes, the compounds of the instant inventioncan be incorporated in the clear coat or both in the clear coat and inthe pigmented base coat.

When water-soluble, water miscible or water dispersible coating aredesired ammonium salts of acid groups present in the resin are formed.Powder coating composition can be prepared by reacting glycidylmethacrylate with selected alcohol components.

The instant benzotriazoles are made by conventional methods forpreparing such compounds. The usual procedure involves the diazotizationof a substituted o-nitroaniline followed by coupling the resultantdiazonium salt with a substituted phenol and reduction of the azobenzeneintermediate to the corresponding desired benzotriazole. The startingmaterials for these benzotriazoles are largely items of commerce or canbe prepared by normal methods of organic synthesis.

While the instant benzotriazoles with their enhanced durability areparticularly suited for automotive coating applications, it iscontemplated that they will also be espeically useful in otherapplications where their enhanced durability is required such as insolar films and the like.

The instant invention also pertains to candle wax compositions whichcomprises

(a) white and unscented, white and scented, dyed and unscented, dyed andscented, dipped and unscented or dipped and scented candle wax, and

(b) an effective stabilizing amount of a benzotriazole of formula I orII as described above alone or in combination with a hindered amine.

An effective amount of benzotriazole alone or plus the hindered amine inthe candle wax is 0.01 to 10% by weight, preferably 0.1 to 2% by weight;and most preferably 0.1 to 0.5% by weight based on the wax. When acombination of benzotriazole and hindered amine are used, the weightratio of benzotriazole to hindered amine is 10:1 to 1:10; preferably 4:1to 1:4; most preferably 2:1 to 1:2 based on the candle wax.

It should be noted that candles contain a host of various components.The base materials may be made up of the following:

paraffin wax,

natural oils,

polyamide plus fatty acid/ester,

fatty acids such as stearin,

opacifiers,

beeswax,

glycerides plus oxidized wax,

alcohols, and

ethylene oligomers.

Candles also contain a number of additives such as the following:

mold release agents,

fragrances,

insect repellants or insecticides,

hardeners,

crystal modifiers,

clarifiers,

guttering reducers,

colorants,

f.p. control agents,

stretchability improvers,

gelling agents,

extrusion aids, and

vortex reducers.

Each of the various components are meant to control or modify theproperties of the candle to insure proper burning, reduce channelling,aid in uniform melting, and the like. The colorants and fragrancesobviously are there to provide the proper color, scent or otheraesthetic appeal.

Of increasing importance are the transparent gel candles which look likeclear glass, but which burn like a classical candle. As is discussed indetail in U.S. Pat. No. 5,879,694, the relevant parts of which areincorporated herein by reference, these gel candles usually contain acopolymer selected from the group consisting of a triblock, radialblock, diblock or multiblock copolymer classically made up of at leasttwo thermodynamically incompatible segments containing both hard andsoft segments. Typical of such block copolymers is KRATON® (ShellChemical Co.) which consists of block segments of styrene monomer unitsand rubber monomer or comonomer units. The most common structure foundin KRATON® D series is a linear ABA block with styrene-butadiene-styrene(SBS) or styrene-isoprene-styrene (SIS).

Candles may also contain other stabilizers such as phenolicantioxidants, phosphites, hydroxylamines and the like, particularlyphenolic antioxidants such as are described above.

The following examples are for illustrative purposes only and are not tobe construed to limit the scope of the instant invention in any mannerwhatsoever.

EXAMPLE 15-Phenyl-2-(2-hydroxy-3-phenyl-5-tert-octylphenyl)-2H-benzotriazole

(A) 3-Nitro-4-acetamido-1,1′-biphenyl

To a mixture of 4-acetamido-1,1′biphenyl (21.1 g, 0.1 mol) and 150 mL ofacetic anhydride maintained between 8° C. and 13° C. is slowly addeddropwise over 32 minutes 12.7 mL of 70% nitric acid. The reactionmixture is added to 600 mL of a mixture of water and ice and theresultant precipitate is collected by filtration. The filter cake iswashed with water and the residue is recrystallized from methanol (800mL) to give 23.6 g of the title compound as a yellow crystalline solidmelting at 129–132° C.

(B) 3-Nitro-4-amino-1,1′-biphenyl

A mixture of potassium hydroxide (2.5 g),3-nitro-4-acetamido-1,1′-biphenyl (23.5 g), prepared in (A) above, water(6 mL) and ethanol (12 mL) is heated at reflux for one hour. Thereaction mixture is cooled to room temperature and then poured into 300mL of a mixture of water and ice. The solid is collected by filtrationand the crude product is recrystallized from methanol (800 mL) to give14.1 g of the title compound as an orange solid melting at 170–172° C.

(C) 4-Phenyl-2-nitrobenzenediazonium Hydrogen Sulfate

To 70 mL of sulfuric acid at 10° C. is added portionwise sodium nitrite(7 g, 0.1 mol). The reaction mixture is warmed to 20° C. to dissolve allthe sodium nitrite and then cooled to 15° C. To the reaction mixture isadded over 30 minutes a suspension of 3-nitro-4-amino-1,1′-biphenyl(7.33 g, 0.034 mol), prepared in (B) above, in 60 mL of acetic acid. Thereaction mixture is stirred for one hour at 10° C. and then to thereaction mixture is added 500 mL of diethyl ether. An exotherm occurs.The mixture is stirred for one hour. The solid formed is removed byfiltration behind a safety shield and washed with diethyl ether to give16.2 g of the title compound as a yellow solid. The solidis dried for1.5 hours at 20° C. under vacuum and stored in a freezer in apolyethylene container until later use. Analysis: IR (nujol) v 1650(N═N), 2250 (N₂ ⁺) cm⁻¹.

(D) 2-Hydroxy-2′nitro-3,4′-diphenyl-5-tert-octylazobenzene

To a solution of sodium hydroxide (12 g, 0.3 mol) and2-phenyl-4-tert-octylphenol (14.1 g, 0.05 mol) in 150 mL of methanolmaintained at 0–5° C. is added portionwise over 1.25 hours4-phenyl-2-nitrobenzenediazonium hydrogen sulfate (30.6 g, 0.065 mol),prepared in (C) above. The reaction mixture is stirred for two hours at0–5° C. Xylene (200 mL) is added to the reaction mixture. The organicphase is separated and extracted with water (4×200 mL). The organicphase is filtered and the solvent removed by distillation under anatmosphere of nitrogen. The residue is purified by flash chromatography(90:10 heptane:ethyl acetate eluent) to give 6.56 g of the titlecompound as a viscous dark red liquid.

(E) 5-Phenyl-2-(2-hydroxy-3-phenyl-5-tert-octylphenyl)-2H-benzotriazole

To a solution of sodium hydroxide (6 g, 0.15 mol) in 8 mL of water isadded 2-hydroxy-2′nitro-3,4′-diphenyl-5-tert-octylazobenzene (6.56 g),prepared in (D) above. The reaction mixture is heated to reflux and thenformadine sulfinic acid (10.8 g, 0.1 mol) is added portionwise over 20minutes. The reaction mixture is heated at reflux for 1.5 hours. To thecooled reaction mixture is added 200 mL of water and the ethanol isremoved under vacuum. The reaction mixture is adjusted to pH 4 withhydrochloric acid. The resultant mixture is extracted twice withmethylene chloride and the combined organic phases are extracted withwater. The organic phase is dried ovdr anhydrous magnesium sulfate, andthe solvent is then removed under vacuum. The residue is recrystallizedsequentially from a mixture of water and methanol, and petroleum etherto give the title compound as a white solid melting at 123–125° C.

EXAMPLE 25-(4-Trifluoromethylphenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

This example illustrates the use of n-propanol as solvent andtriphenylphosphine as a ligand in the Suzuki reaction to make theinstant compound.

A flask, equipped with a mechanical stirrer and an inert atmosphere witha FIRESTONE® valve, containing a mixture of5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole(5.21 g, 0.01 mol), 4-trifluoromethylphenylboronic acid (1.99 g, 0.0105mol) and 250 mL of n-propanol is evacuated and filled three times withnitrogen. To this mixture is then added palladium (II) diacetate (0.090g, 0.0004 mol), triphenylphosphine (0.315 g, 0.0012 mol), 6 mL of 2Msodium carbonate (1.27 g, 0.012 mol) and 10 mL of water. The flask isthen evacuated and filled with nitrogen three times. The reactionmixture is stirred for 15 minutes at room temperature and then heated to85° C. The reaction mixture is heated at 85° C. for four hours and thenallowed to cool to room temperature. The solvent is removed under vacuumand the residue is partitioned between diethyl ether (250 mL) and water(100 mL). The organic phase is separated and extracted sequentially with5% aqueous sodium bicarbonate (100 mL) and saturated aqueous sodiumchloride (100 mL). The organic phase is dried over anhydrous sodiumsulfate and the volatiles are removed under vacuum. The residue isrecrystallized from isopropanol (250 mL) to give 3.59 g (61% yield) of alight yellow solid. An analytical sample is prepared by dissolving theproduct in toluene (25 mL) and treating the resultant solution withactivated carbon followed by chromatography (silical gel; ethyl acetateeluent) to give 2.87 g of the tide compound as a pale yellow solid.Further purification is effected by sublimation to give a productmelting at 146–147.5° C.

¹Hnmr (CDCl₃; 499.8494 MHz) δ 0.84 (s, 9H); 1.52 (s, 6H); 1.83 (s, 6H);1.86 (s, 2H); 7.15–7.30 (overlapping multiplets, 5H); 7.65 (d, 1H); 7.69(d, 1H); 7.77 (multiplet, 4H); 7.96 (d, 1H); 8.05 (d, 1H); 8.36 (d, 1H);11.33 (s, 1H); ¹⁹Fnmr (CDCl₃; 282.3300 MHz) δ−69.04; Analysis: Calcd forC₃₆H₃₈F₃N₃O: C, 73.82; H, 6.54; N, 7.17. Found: C, 73.82; H, 6,46; N,7.07.

EXAMPLE 35-(4-Trifluoromethylphenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

This example illustrates the use of isopropanol as solvent andtriphenylphosphine as a ligand in the Suzuki reaction to make theinstant compound.

The procedure of Example 2 is followed using5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole(1.04 g, 0.002 mol), 4-trifluoromethylphenylboronic acid (0.40 g, 0.0021mol), palladium (II) diacetate (0.045 g, 0.0002 mol), triphenylphosphine(0.160 g, 0.0006 mol), 1.2 mL of 2M sodium carbonate (0.25 g, 0.0024mol), 2 mL of water and 50 mL of isopropanol at 79° C. for five hours togive 0.97 g (83% yield) of the title compound as a solid identical tothat prepared in Example 2.

EXAMPLE 45-(4-Trifluoromethylphenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

This example illustrates the use of dioxane as solvent,2-(di-tert-butylphosphino)biphenyl as a ligand, and potassium fluoridein place of sodium carbonate in the Suzuki reaction to make the instantcompound.

The procedure of Example 2 is followed using5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole(1.04 g, 0.002 mol), 4-trifluoromethylphenylboronic acid (0.57 g, 0.003mol), palladium (II) diacetate (0.045 g, 0.0002 mol),2-(di-tert-butyl-phosphino)biphenyl (0.119 g, 0.0004 mol), potassiumfluoride (0.34 g, 0.0006 mol) and 30 mL of dioxane at 67° C. for 1.25hours to give 0.46 g (39% yield) of the title compound as a solididentical to that prepared in Example 2.

EXAMPLE 55-(4-Trifluoromethylphenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

This example illustrates the use of dioxane as solvent,1,1′-bis[2,4,8,10-tetrakis(tert-butyl)-dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]ferroceneas a ligand, and potassium fluoride in place of sodium carbonate in theSuzuki reaction to make the instant compound.

The procedure of Example 2 is followed using5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole(1.04 g, 0.002 mol), 4-trifluoromethylphenylboronic acid (0.57 g, 0.003mol), palladium (II) diacetate (0.045 g, 0.0002 mol),1,1′-bis[2,4,8,10-tetrakis(tert-butyl)-dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]ferrocene(0.425 g, 0.0004 mol), potassium fluoride (0.34 g, 0.0006 mol) and 30 mLof dioxane at 67° C. for 1.25 hours to give 0.84 g (72% yield; drycolumn chromatography; 9:1 heptane:ethyl acetate eluent) of the titlecompound as a solid identical to that prepared in Example 2.

EXAMPLE 65-(3-Trifluoromethylphenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

This example illustrates the use of isopropanol as solvent andtriphenylphosphine as a ligand in the Suzuki reaction to make theinstant compound.

The procedure of Example 2 is followed using5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole(1.04 g, 0.002 mol), 3-trifluoromethylphenylboronic acid (0.40 g, 0.0021mol), palladium (II) diacetate (0.045 g, 0.0002 mol), triphenylphosphine(0.160 g, 0.0006 mol), 1.2 mL of 2M sodium carbonate (0.25 g, 0.0024mol), 2 mL of water and 50 mL of isopropanol at 79° C. for five hours.The residue is purified by recrystallization from isopropanol (20 mL)followed by chromatography (acid alumina; 9:1 heptane:ethyl acetateeluent) to give 0.80 g (68% yield) of the title compound as a lightyellow solid melting at 138–139.5° C.

¹Hnmr (CDCl₃; 499.8494 MHz) δ 0.81 (s, 9H); 1.52 (s, 6H); 1.83 (s, 6H);1.86 (s, 2H); 7.15–7.32 (overlapping multiplets, 5H); 7.62 (dd, 1H);7.64 (d, 1H); 7.67 (d, 1H); 7.69 (dd, 1H); 7.84 (d, 1H); 7.91(unresolved d, 1H); 7.95 (d, 1H); 8.05 (d, 1H); 8.36 (d, 1H); 11.33 (s,1H); ¹⁹Fnmr (CDCl₃; 282.3300 MHz) δ −69.04; MS (DIP) m/z 585 (M⁺)Analysis: Calcd for C₃₆H₃₈F₃N₃O: C, 73.82; H, 6.54; N, 7.17. Found: C,73.48; H, 6,46; N, 6.92.

EXAMPLE 75-(3-Trifluoromethylphenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

This example illustrates the use of n-propanol as solvent andtriphenylphosphine as a ligand in the Suzuki reaction to make theinstant compound.

The procedure of Example 2 is followed using5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole(5.21 g, 0.01 mol), 3-trifluoromethylphenylboronic acid (1.99 g, 0.0105mol), palladium (II) diacetate (0.090 g, 0.0004 mol), triphenylphosphine(0.315 g, 0.0012 mol), 6 mL of 2M sodium carbonate (1.27 g, 0.012 mol),10 mL of water and 250 mL of n-propanol at 84° C. for 3.5 hours to give5.17 g (88% yield) of the title compound as a solid identical to thecompound prepared in Example 6.

EXAMPLE 85-(2-Trifluoromethylphenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

This example illustrates the use of isopropanol as solvent andtriphenylphosphine as a ligand in the Suzuki reaction to make theinstant compound.

The procedure of Example 2 is followed using5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole(2.60 g, 0.005 mol), 2-trifluoromethylphenylboronic acid (0.997 g,0.00525 mol), palladium (II) diacetate (0.045 g, 0.0002 mol),triphenylphosphine (0.157 g, 0.0006 mol), 3 mL of 2M sodium carbonate(0.64 g, 0.006 mol), 5 mL of water and 200 mL of n-propanol at 91° C.for two hours. The residue is purified by chromatography (tolueneeluent) followed by recrystallization from isopropanol (50 mL) to give1.85 g (63% yield) of the title compound as a yellow solid melting at133.5–136° C.

¹Hnmr (CDCl₃; 499.8494 MHz) δ 0.84 (s, 9H); 1.52 (s, 6H); 1.83 (s, 6H);1.86 (s, 2H); 7.15–7.32 (overlapping multiplets, 5H); 7.40 (overlappingd, 2H); 7.53 (dd, 1H); 7.61 (dd, 1H); 7.64 (d, 1H); 7.80 (multiplet,2H); 7.88 (d, 1H); 8.36 (d, 1H); 11.35 (s, 1H); ¹⁹Fnmr (CDCl₃; 282.3300MHz) δ −63.4; MS (DIP) m/z 585 (M⁺)

EXAMPLE 95-Phenyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

(A) 2-Hydroxy-2′nitro-3-α-cumyl-4′-phenyl-5-tert-octylazobenzene

The procedure of Example 1 (D) is followed using sodium hydroxide (4 g,0.1 mol), methanol (100 mL), 4-phenyl-2-nitrobenzenediazonium hydrogensulfate (16 g, 0.034 mol) and 2-α-cumyl-4-tert-octylphenol (8.1 g, 0.028mol) to give the title compound as a dark red solid melting at 176–179°C.

(B) 5-Phenyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

The procedure of Example 1 (E) is followed using sodium hydroxide (4 g,0.1 mol), 5 mL of water,2-hydroxy-2′nitro-3-α-cumyl-4′-phenyl-5-tert-octylazobenzene (4 g,0.0072 mol) and fomamidine sulfinic acid (6.5 g, 0.06 mol) to give thetitle compound as a pale yellow crystalline solid melting at 137–139° C.

¹Hnmr (CDCl₃) δ 0.84 (s, 9H); 1.52 (s, 6H); 1.83 (s, 6H); 1.86 (s, 2H);7.15–7.32 (overlapping multiplets, 5H); 7.41 (t, 1H); 7.50 (dd, 2H);7.63 (d, 1H); 7.67 (d, 2H); 7.71 (dd, 1H); 7.92 (d, 1H); 8.01 (d, 1H);8.35 9D, 1h); 11.41 (s, 1H). Analysis: Calcd for C₃₅H₃₉N₃O: C, 81.20; H,7.59; N, 8.12. Found: C, 80.97; H, 7.54; N, 8.07.

EXAMPLE 105-Phenyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

The procedure of Example 2 is followed using5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole(5.21 g, 0.01 mol), phenylboronic acid (1.28 g, 0.0105 mol), palladium(II) diacetate (0.090 g, 0.0004 mol), triphenylphosphine (0.315 g,0.0012 mol), 6 mL of 2M sodium carbonate (1.27 g, 0.012 mol), 10 mL ofwater and 250 mL of isopropanol at 84° C. for 3.5 hours. The titlecompound is obtained as a solid which is identical to that prepared inExample 9.

EXAMPLE 115-(3,5-Di-trifluoromethylphenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

The procedure of Example 2 is followed using5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole1.04 g, 0.002 mol), 3,5-di-trifluoromethylphenylboronic acid (0.54 g,0.0021 mol), palladium (II) diacetate (0.045 g, 0.0002 mol),triphenylphosphine (0.160 g, 0.0006 mol), 1.2 mL of 2M sodium carbonate(0.25 g, 0.0024 mol), 2 mL of water and 50 mL of isopropanol at 79° C.for five hours. The residue is purified by recrystallizationsequentially from isopropanol (20 mL) and acetonitrile (10 mL) to give0.44 g (34% yield) of the title compound as a light yellow solid meltingat 79–81° C.

¹Hnmr (CDCl₃; 499.8494 MHz) δ 0.84 (s, 9H); 1.52 (s, 6H); 1.83 (s, 6H);1.86 (s, 2H); 7.16–7.32 (overlapping multiplets, 5H); 7.66 (d, 1H); 7.69(dd, 1H); 7.92 (d, 1H); 8.00 (d, 1H); 8.09 (d, 2H); 8.10 (d, 1H); 8.36(d, 1H); 11.25 (s, 1H); ¹⁹Fnmr (CDCl₃; 282.3300 MHz) δ −69.4; Analysis:Calcd for C₃₇H₃₇F₆N₃O: C, 67.98; H, 5.71; N, 6.43. Found: C, 67.66; H,5.66; N, 6.34.

EXAMPLE 125-(1,1′-Biphenyl-4-yl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

The procedure of Example 2 is followed using5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole1.04 g, 0.002 mol), (1,1′-biphenyl-4-yl)boronic acid (0.42 g, 0.0021mol), palladium (II) diacetate (0.045 g, 0.0002 mol), triphenylphosphine(0.160 g, 0.0006 mol), 1.2 mL of 2M sodium carbonate (0.25 g, 0.0024mol), 2 mL of water and 50 mL of isopropanol at 79° C. for five hours.The residue is purified by recrystallization sequentially from a mixtureof toluene (10 mL) and ethyl acetate (100 mL), and heptane (10 mL) togive 0.46 g (39% yield) of the title compound as an off-white solidmelting at 181–183° C.

¹Hnmr (CDCl₃; 499.8494 MHz) δ 0.84 (s, 9H); 1.53 (s, 6H); 1.83 (s, 6H);1.86 (s, 2H); 7.13–7.32 (overlapping multiplets, 5H); 7.39 (t, 1H); 7.49(dd, 2H); 7.63 (d, 1H); 7.67 (d, 2H); 7.75 (m, 4H); 7.76 (dd, 1H); 7.93(d, 1H); 8.07 (d, 1H); 8.36 (d, 1H); 11.40 (s, 1H); Analysis: Calcd forC₄₁H₄₃F₃N₃O: C, 82.93; H, 7.30; N, 7.08. Found: C, 83.12; H, 7.23; N,6.88.

EXAMPLE 135-(4-Cyanophenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

The procedure of Example 2 is followed using5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole1.04 g, 0.002 mol), 4-cyanophenylboronic acid (0.42 g, 0.0021 mol),palladium (II) diacetate (0.045 g, 0.0002 mol), triphenylphosphine(0.160 g, 0.0006 mol), 1.2 mL of 2M sodium carbonate (0.25 g, 0.0024mol), 2 mL of water and 50 mL of isopropanol at 79° C. for five hours.The residue is purified by recrystallization from heptane followed bydry-column chromatography (9:1 heptane:ethyl acetate eluent) to give0.18 g (17% yield) of the title compound as a light yellow crystallinesolid melting at 163–164.5° C.

¹Hnmr (CDCl₃; 499.8494 MHz) δ 0.84 (s, 9H); 1.52 (s, 6H); 1.83 (s, 6H);1.86 (s, 2H); 7.15–7.32 (overlapping multiplets, 5H); 7.65 (d, 1H); 7.67(dd, 1H); 7.76 (d, 2H); 7.79 (d, 2H); 7.97 (d, 1H); 8.05 (d, 1H); 8.35(d, 1H); 11.30 (s, 1H); MS (DIP) m/z 542 (M⁺) Analysis: Calcd forC₃₆H₃₈N₄O: C, 79.67; H, 7.06; N, 10.32. Found: C, 79.79; H, 7.12; N,10.19.

EXAMPLE 145-Bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benwtriazole

This compound is an important intermediate for the preparation of theinstant compounds by the Suzuki reaction by reaction with variousarylboronic acids or esters.

(A) 2-Hydroxy-2′nitro-3-α-cumyl-4′-bromo-5-tert-octylazobenzene

Diazotization and coupling: 96% Sulfuric acid (243 g) is charged to a 2Ljacketed reactor and the internal temperature is adjusted to 20° C. 40%(wt/wt) nitrosylsulfuric acid (335.4 g in sulfuric acid, 1.06 mol) isadded via an addition funnel keeping the internal temperature below 20°C. At the end of this dilution step, the solution is cooled to 0° C. and217 g of 92.1% pure 4-bromo-2-nitroaniline (0.921 mol) is added inportions keeping the internal temperature between 15–20° C. The reactionmixture is stirred at room temperature for five hours. Water (674 g) isadded over a two-hour period while keeping the internal tempearature at0–5° C. The solution is filtered through a coarse funnel and stored at0° C. Titration of the diazo solution shows an sulfuric acid assay of31.8% and a diazo assay of 17.9% (a yield of 86.2% of diazo compoundbased on the 4-bromo-2-nitroaniline).

In a 1L jacketed reactor is added 94.9 g of 96% pure2-α-cumyl-4-tert-octylphenol (0.281 mol) and 249.5 g of xylene followedby 4.1 g of HOSTAPUR® SAS 93. The mixture is dissolved at 28° C. and thetemperature held there. The diazonium salt solution prepared above (723g, 0.397 mol) is added to this solution over a period of six hours. Atthe end of the addition period, the transfer line is rinsed with 10.8 gof water and the reaction mixture is stirred for another 30 minutes. Thereaction temperature is raised to 60° C. and stirring stopped. Themixture divided into two phases which are separated. 370.3 g of a xylenesolution of2-hydroxy-2′-nitro-3-α-cumyl-4′-phenyl-5-tert-octylazobenzene isobtained. The xylene is removed under vacuum and methanol is added tocrystallize the product.

¹Hnmr (CDCl₃; 499.8494 MHz) δ 0.83 (s, 9H); 1.44 (s, 6H); 1.78 (s, 2H);1.79 (s, 6H); 7.13–7.28 (overlapping multiplets, 5H); 7.62 (d, 1H); 7.68(d, 1H); 7.79 (dd, 1H); 7.85 (d, 1H); 8.19 (d, 1H); 12.94 (s, 1H).

(B) 5-Bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole

To 2-butanol (200 mL) and sodium hydroxide (4.8 g, 0.1203 mol) at 94° C.in a 2L Swiss reaction is added dropwise a solution of2-hydroxy-2′nitro-3-α-cumyl-4′-phenyl-5-tert-octylazobenzene (24.4 g,0.043 mol) and 2,3-dichloro-1,4-naphthoquinone (1.14 g, 0.005 mol) inmethyl ethyl ketone (60 mL) over a period of 1.5 hours while maintainingthe temperature of the reaction mixture over 90° C. Water and methylethyl ketone distill off during this period. After the reaction mixtureis held for one hour at about 90° C., the reduction is complete as seenby a sample tested by HPLC. The reaction mixture is cooled to 30° C. and31 mL of 30% sulfuric acid is added all at once. After further coolingto 5° C., the product precipitates along with a mixture of salts. Theprecipitate is isolated by filtration and freed of salts by repeatedwashing with water. Organic impurities are removed by washing with 200mL of cold methanol. The title compound is obtained after drying in ayield of 73% (16.4 g) as a light beige solid melting at 113–117° C.

¹Hnmr (CDCl₃; 499.8494 MHz) δ 0.83 (s, 9H); 1.51 (s, 6H); 1.81 (s, 6H);1.85 (s, 2H); 7.15–7.30 (overlapping multiplets, 5H); 7.51 (dd, 1H);7.64 (d, 1H); 7.75 (d, 1H); 8.04 (d, 1H); 8.31 (d, 1H); 11.15 (s, 1H).

EXAMPLE 155-(4-Methoxyphenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

The procedure of Example 2 is followed using5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole1.56 g, 0.0105 mol), 4-methoxyphenylboronic acid (1.56 g, 0.0105 mol),palladium (II) diacetate (0.090 g, 0.0004 mol), triphenylphosphine(0.315 g, 0.0012 mol), 6 mL of 2M sodium carbonate (1.27 g, 0.0012 mol),10 mL of water and 250 mL of isopropanol at 90.5° C. for one hour. Theresidue is purified by dry-column flash chromatography (toluene eluent)and recrystallization from heptane (2×) to give 2.00 g (36.5% yield) ofthe title compound as light yellow crystals melting at 129–131° C.

¹Hnmr (CDCl₃; 499.8494 MHz) δ 0.84 (s, 9H); 1.52 (s, 6H); 1.83 (s, 6H);1.86 (s, 2H); 3.89 (s, 3H); 7.03 (d, 2H); 7.14–7.32 (overlappingmultiplets, 5H); 7.61 (d, 2H); 7.62 (d, 1H); 7.68 (dd, 1H); 7.89 (dd,1H); 7.95 (multiplet, 1H); 8.34 (d, 1H); 11.41 (s, 1H); Analysis: Calcdfor C₃₆H₄₁N₃O₂: C, 78.94; H, 7.54; N, 7.67. Found: C, 79.11; H, 7.43; N,7.59.

EXAMPLE 161,4-Bis[2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazol-5-yl]benzene

The procedure of Example 2 is followed using5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole(5.73 g, 0.011 mol), 1,4-phenylenebis(boronic acid) (0.83 g, 0.005 mol),palladium (II) diacetate (0.090 g, 0.0004 mol), triphenylphosphine(0.315 g, 0.0012 mol), 6 mL of 2M sodium carbonate (1.27 g, 0.012 mol),10 mL of water and 250 mL of isopropanol at 88° C. for three hours. Theresidue is purified by dry-column flash chromatography (toluene eluent)and recrystallization from heptane to give 2.58 g (53.9% yield) of thetitle compound as light yellow crystals melting at 247–249° C.

(Dry-column flash chromatography is described by J. Leonard, B. Lygo andG. Proctor, in “Advanced Practical Organic Chemistry”, 2nd Edition,Blackie Academic & Professional, London, 1965, pp 215–216.)

¹Hnmr (CDCl₃; 499.8494 MHz) δ 0.84 (s, 18H); 1.53 (s, 12H); 1.84 (s,12H); 1.87 (s, 4H); 7.15–7.34 (overlapping multiplets, 10H); 7.64 (d,2H); 7.77 (dd, 2H); 7.80 (s, 4H); 7.95 (d, 2H); 8.09 (d, 2H); 8.36 (d,2H); 11.40 (s, 2H). Analysis: Calcd for C₆₄H₇₂N₆O₂: C, 80.30; H, 7.58;N, 8.78. Found: C, 80.20; H, 7.63; N, 8.59.

EXAMPLE 175-(4-Methoxyphenyl)-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole

The procedure of Example 2 is followed using5-chloro-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole3.58 g, 0.01 mol), 4-methoxyphenylboronic acid (3.04 g, 0.002 ml),palladium (II) diacetate (0.224 g, 0.001 mol),2-(dicyclohexylphosphino)biphenyl (0.701 g, 0.002 mol), potassiumfluoride (1.16 g, 0.02 mol) and 200 mL of dioxane at 88° C. for twohours. The residue is purified by dry-column flash chromatography(silica gel, 93:5 heptane:ethyl acetate eluent) followed by dissolvingin 50 mL of toluene and extraction with 5% aqueous sodium bicarbonate(20 mL) and saturated sodium chloride solution (20 mL). The toluenesolution is dried over anhydrous sodium sulfate and the solvent removedunder vacuum to give 0.60 g (14% yield) of the title compound as lightyellow solid.

¹Hnmr (CDCl₃; 499.8494 MHz) δ 1.42 (s, 9H); 1.53 (s, 9H); 3.90 (s, 3H);7.05 (d, 2H); 7.44 (d, 1H); 7.64 (d, 2H); 7.73 (dd, 1H); 7.98 (d, 1H);8.04 (d, 1H); 8.31 (d, 1H); 11.79 (s, 1H). MS (DIP) 429 (M⁺).

EXAMPLE 185-(4-Trifluoromethylphenyl)-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole

The procedure of Example 2 is followed using5-chloro-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole3.58 g, 0.01 mol), 4-trifluoromethylphenylboronic acid (2.85 g, 0.015ml), palladium (II) diacetate (0.224 g, 0.001 mol),2-(di-tert-butyl-phosphino)biphenyl (0.596 g, 0.002 mol), potassiumfluoride (1.16 g, 0.02 mol) and 200 mL of dioxane at 88° C. for twohours. The residue is purified by dry-column flash chromatography(silica gel, 93:5 heptane:ethyl acetate eluent) to give 0.64 g (13.7%yield) of the title compound as light yellow solid. MS (DIP) 467 (M⁺).Analysis: Calcd for C₃₆H₄₁N₃O₂: C, 78.94; H, 7.54; N, 7.67. Found: C,79.11; H, 7.43; N, 7.59.

EXAMPLE 19 Polycarbonate

The durability of representative instant benzotriazoles in thermoplasticsubstrates is determined by incorporating various test compounds intosolvent cast films of polycarbonate resins. The free standing films aremounted into cardboard holders, secured in metal frames and exposed inan Atlas C165 Xenon-arc Weather-Ometer under dry conditions according toASTM G26. Loss of UV absorber is determined by monitoring the loss ofdiagnostic UV absorption.

Polycarbonate flake (LEXAN® 145, General Electric) is dissolved inmethylene chloride at room temperature along with between 1 and 3% byweight of test benzotriazole, based on the polycarbonate. Films are castusing a calibrated drawdown bar to prepare 1 mil thick film afterdrying.

The instant compounds are particularly efficacious when used inthermoplastic compositions, such as polycarbonate. This is shown by thereduction in absorbance loss after exposure to actinic radiation.

EXAMPLE 20 Polycarbonate

Polycarbonate films of about 1 mil thickness and containing a UVabsorber are prepared by dissolving polycarbonate granules (LEXAN® 145,General Electric) and UV absorbers in methylene chloride and casting thefilms on a glass plate using a drawdown bar. The films are exposed for750 hours in a Xenon Arc Weather-Ometer according to ASTM G26 testmethod and the color change (ΔYI) versus that for unexposed films arerecorded below. The color measurements (yellowness index—YI) are carriedout on an ACS spectrophotometer, small area view, spectral componentincluded d/8, D65, 10° observer, YI 1925 for unexposed and exposedsamples after 750 hours.

The instant compounds are particularly efficacious when used inthermoplastic compositions, such as polycarbonate. This is shown by thereduction of yellowing (ΔYI) after exposure to actinic radiation.

EXAMPLE 21 Poly(methyl methacrylate)

The durability of representative instant benzotriazoles in thermoplasticsubstrates is determined by incorporating various test compounds intosolvent cast films of a poly(methyl methacrylate) (PMMA) resin. The freestanding films are mounted into cardboard holders, secured in metalframes and exposed in an Atlas C165 Xenon-arc Weather-Ometer under dryconditions according to ASTM G26. Loss of UV absorber is determined bymonitoring the loss of diagnostic UV absorption as described earlier.Performance is measured by a change in color or the physical integrityof the film, or in loss of absorbance of the UV absorber at λmax.

Poly(methyl methacrylate), medium molecular weight, Aldrich, isdissolved in methylene chloride at room temperature along with between 1and 3% by weight of test benzotriazole, based on the PMMA resin. Filmsare cast using a calibrated drawdown bar to prepare 1 mil thick filmafter drying.

The instant compounds are particularly efficacious when used inthermoplastic compositions, such as poly(methyl methacrylate). This isshown by the reduction in absorbance loss after exposure to actinicradiation.

EXAMPLE 22 Incorporation into Photographic Layers

A gelatin coat of the following composition (per m²) is applied in thecustomary manner to a polyester base.

Components Amount Gelatin 1200 mg Tricresyl Phosphate  510 mg Hardener* 40 mg Wetting Agent**  100 mg Test UV Absorber  400 mg *potassium saltof 2-hydroxy-4,6-dichloro-s-triazine **sodium4,8-diisobutylnaphthalene-2-sulfonate

The gelatin coats are dried at 20° C. for seven days.

When the instant UV absorbers are used, clear transparent coats areobtained which are suitable for photographic recording material forexample as a UV filter coat. This is seen by measuring the % Change inInitial Optical Density (2.0) after UV exposure. The instant compoundswhen used in a photographic layer are extremely photostable.

EXAMPLE 23 Automotive Coating Compositions

To ascertain the effect on thermal durability and loss rate from a highsolids thermoset acrylic coating containing an instant benzotriazole UVabsorber, the following tests are carried out.

A high solids thermoset acrylic clear coat is prepared by mixing anexperimental acrylic polyol resin and hexamethoxymethylmelamine(Resimene® 747, Monsanto) at a solids ratio of 60/40. The dodecylbenzenesulfonic acid catalyst (Nacure® 5225; King Industries) is added at 0.70%by weight. A flow aid Modaflow® (Monsanto) is added at 0.25% by weightto form a model acrylic melamine resin system.

The model clear coat is reduced with xylene to a viscosity of 26–27second using a Zahn #2 cup and applied via a conventional air spray at50 psi (3.5 Kg/cm²) over a 1″×3″ (2.54 cm×7.62 cm) quartz slide. Cure isachieved by baking the slide for 30 minutes at 260° F. (127° C.). Theclear coat is stabilized with 1% by weight of a hindered amine lightstabilizer, bis-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,(TINUVIN® 123, Ciba). The various test benzotriazole UV absorbers areincorporated at the 5 mmol % by weight in the clear coat. The filmthickness on the quartz slides range from 1.15 to 1.41 mils (0.029 to0.036 mm).

The films on the quartz slides are weathered according to the followingconditions in Xenon Arc Weather-Ometer with a controlled irradiance at6500 W, using inner quartz and outer borosilicate S-type filter. Theirradiation cycle is as follows: 40 minutes of straight irradiation withno water spray, followed by 20 minutes of light plus front spray,followed by 60 minutes of light irradiation and finally by 60 minutesdart plus rear spray (condensation). The setting is at 0.55 W/M² at 340nm, 1.98 kJ/hour. In the light cycle the black panel temperature iscontrolled at 70±2° C. The relative humidity in the light cycle is inthe range of 50–55% and in the dark cycle 100%. The absorbance of thelong wavelength UV band as a function of Xenon arc weathering hours arerecorded.

To follow the loss of UV absorbers from the clear coats, UV spectra aremeasured initially and after weathering at regular time intervals. TheUV spectrophotometer measures absorbance linearly up to 5.5 absorbanceunits using a reference beam attenuation technique.

It is assumed that the degradation products from the UV absorber do notcontribute to the UV spectrum. This is tested by following the ratio ofabsorbance of the band at about 300 nm and the band at about 340 nm. Theratio does not change upon weathering the sample. This suggests that theUV spectrum of the weathered films correspond to the amount of UVabsorber remaining in the film with very little if any contribution tothe spectrum by photo degradants.

Representative benzotriazole test compounds are incorporated into a highsolid thermoset acrylic melamine resin at a concentration of 3% byweight to give equal molar concentrations of the test benzotriazole inequal film thickness and sufficient to give a starting absorbance ofapproximately 2.0 absorbance units.

The instant benzotriazoles are especially durable in automotive coatingsas judged by low loss rates.

EXAMPLE 24 Color Change of a White Unscented Candle Wax UnderFluorescent Lamp Exposure

A variety of different stabilizers are evaluated in a white unscentedcandle wax under fluorescent lamp exposure. The stabilizers include acompound of Example 2 alone or with a hindered amine likebis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, TIUVIN® 292, CIBA orbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, TINUVIN®123, CIBA. The ΔE values represent the change in color after exposure. Alow ΔE value indicates less change in color and is highly desired.

The instant compound alone or with the hindered amine provides excellentprotection to the white unscented candle wax from discoloration.

EXAMPLE 25 Color Fade of Green Scented Candle Wax Under UV Lamp Exposure

A variety of different stabilizers are evaluated in green scented candlewax obtained from the Candle Corporation of America under UV lampexposure at 368 nm wavelength. The stabilizers include a compound ofExample 1 alone or with a hindered amine likebis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, TINUVIN® 292, CIBA orbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, TINUVIN®123, CIBA. The ΔE values represent the change in color after exposure. Alow ΔE value indicates less change in color and is highly desired.

The instant compound alone or with the hindered amine provides excellentprotection to the green scented candle wax from dye fade.

EXAMPLE 26 Color Fade of a Blue Unscented Candle Wax Under UV LampExposure

A variety of different stabilizers are evaluated in blue unscentedcandle wax under UV lamp exposure at 368 nm wavelength. The stabilizersinclude a compound of Example 1 alone or with a hindered amine likebis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, TINUVIN® 292, CIBA orbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, TINUVIN®123, CIBA. The ΔE values represent the change in color after exposure. Alow ΔE value indicates less change in color and is highly desired.

The instant compound alone or with the hindered amine provides excellentprotection to the blue unscented candle wax from dye fade.

EXAMPLE 27 Color Fade of Pink Scented Candle Wax Under Fluorescent LampExposure

Different stabilizers are evaluated in pink scented candle wax obtainedfrom the Candle-Lite Corporation under fluorescent lamp exposure. The ΔEvalues represent the change in color after the indicated days ofexposure. A low ΔE value indicates less change in color and is highlydesired.

ΔE after Sample* (wt % add) 8.9 days 11.8 days 22.3 days Blank (no add)8.10 10.22 12.12 A (0.3%) 8.72 10.48 12.91 F (0.3%) 6.75 6.50 8.58 C(0.15%) + D 2.07 4.37 5.94 (0.15%) A (0.15%) + B 3.18 2.20 2.79 (0.15%)E (0.15%) + B 4.21 3.24 2.13 (0.15%) F (0.15%) + G 1.77 2.49 4.16(0.15%) *A is bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, TINUVIN ® 123, CIBA). B is5-(4-trifluoromethylphenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,Compound of Example 2. C is2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, TINUVIN ® 329, CIBA.D is 4-octyloxy-2-hydroxybenzophenone, CHIMASSORB ® 81, CIBA. E is1,3,5-tris[N-cyclohexyl-N-(2,2,6,6-tetramethylpiperazin-3-on-4-yl)amino]-s-triazine,GOODRITE ® 3150, Goodrich. F is bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate, TINUVIN ® 292, CIBA. G is1,4-bis[2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazol-5-yl]benzene,Compound of Example 16.

These data show that a hindered amine in combination with an instant UVabsorber protects the pink scented candle wax far better than thehindered amine or a UV absorber alone.

EXAMPLE 28 Color Fade of Pink Scented Candle Wax Under UV Lamp Exposure

A variety of different stabilizers are evaluated in pink scented candlewax obtained from the Candle-Lite Corporation under UV lamp exposure.The ΔE values represent the change in color after the indicated days ofexposure. A low ΔE value indicates less change in color and is highlydesired.

ΔE after Sample* (wt % add) 7.6 days 13.5 days 36.7 days Blank (no add)16.16 16.44 20.27 A (0.3%) 13.93 15.20 15.88 F (0.3%) 14.79 16.41 17.53C (0.15%) + D 8.93 7.72 9.62 (0.15%) F (0.15%) + G 2.99 3.72 5.59(0.15%) A (0.15%) + B 1.54 1.67 3.08 (0.15%) E (0.15%) + B 3.19 2.762.10 (0.15%) *A is bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, TINUVIN ® 123, CIBA). B is5-(4-trifluoromethylphenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,Compound of Example 2. C is2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, TINUVIN ® 329, CIBA.D is 4-octyloxy-2-hydroxybenzophenone, CHIMASSORB ® 81, CIBA. E is1,3,5-tris[N-cyclohexyl-N-(2,2,6,6-tetramethylpiperazin-3-on-4-yl)amino]-s-triazine,GOODRITE ® 3150, Goodrich. F is bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate, TINUVIN ® 292, CIBA. G is1,4-bis[2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazol-5-yl]benzene,Compound of Example 16.

These data show that a hindered amine in combination with an instant UVabsorber protects the pink scented candle wax far better thanconventional UV absorbers or a hindered amine alone.

EXAMPLE 29 Color Fade of Gray Scented Candle Wax Under Fluorescent LampExposure

A variety of different stabilizers are evaluated in gray scented candlewax obtained from the Candle-Lite Corporation under fluorescent lampexposure. The ΔE values represent the change in color after theindicated days of exposure. A low ΔE value indicates less change incolor and is highly desired.

ΔE after Sample* (wt % add) 4.9 days 10.9 days 33.9 days Blank (no add)9.66 11.97 16.01 A (0.3%) 9.67 10.89 11.32 F (0.3%) 4.88 6.16 7.55 C(0.15%) + D 1.56 4.33 8.52 (0.15%) A (0.15%) + B 1.74 2.01 4.50 (0.15%)A (0.15%) + G 0.80 1.99 4.09 (0.15%) F (0.15%) + B 1.21 1.24 3.42(0.15%) *A is bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, TINUVIN ® 123, CIBA). B is5-(4-trifluoromethylphenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,Compound of Example 2. C is2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, TINUVIN ® 329, CIBA.D is 4-octyloxy-2-hydroxybenzophenone, CHIMASSORB ® 81, CIBA. F isbis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, TINUVIN ® 292, CIBA.G is1,4-bis[2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazol-5-yl]benzene,Compound of Example 16.

These data show that a hindered amine in combination with an instant UVabsorber protects the gray scented candle wax far better thanconventional UV absorbers or a hindered amine alone.

EXAMPLE 30 Color Fade of Gray Scented Candle Wax Under UV Lamp Exposure

A variety of different stabilizers are evaluated in gray scented candlewax obtained from the Candle-Lite Corporation under UV lamp exposure.The ΔE values represent the change in color after the indicated days ofexposure. A low ΔE value indicates less change in color and is highlydesired.

ΔE after Sample* (wt % add) 2.8 days 8.9 days 22.6 days Blank (no add)22.20 28.98 30.07 A (0.3%) 20.83 27.37 25.37 F (0.3%) 23.88 26.40 25.38C (0.15%) + D 2.30 7.06 10.96 (0.15%) F (0.15%) + G 1.98 3.68 4.89(0.15%) A (0.15%) + B 1.10 2.58 4.14 (0.15%) F (0.15%) + B 1.01 2.183.58 (0.15%) *A is bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, TINUVIN ® 123, CIBA). B is5-(4-trifluoromethylphenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,Compound of Example 2. C is2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, TINUVIN ® 329, CIBA.D is 4-octyloxy-2-hydroxybenzophenone, CHIMASSORB ® 81, CIBA. F isbis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, TINUVIN ® 292, CIBA.G is1,4-bis[2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazol-5-yl]benzene,Compound of Example 16.

These data show that a hindered amine in combination with an instant UVabsorber protects the gray scented candle wax far better thanconventional UV absorbers or a hindered amine alone.

EXAMPLE 31 Color Fade of White Scented Candle Wax Under Fluorescent LampExposure

A variety of different stabilizers are evaluated in white scented candlewax obtained from the Candle-Lite Corporation under fluorescent lampexposure. The ΔE values represent the change in color after theindicated days of exposure. A low ΔE value indicates less change incolor and is highly desired.

ΔE after Sample* (wt % add) 4.0 days 14.7 days 33.0 days Blank (no add)27.56 33.74 34.68 A (0.3%) 13.31 22.24 26.35 F (0.3%) 21.46 30.91 32.06C (0.15%) + D 9.39 17.68 21.24 (0.15%) F (0.15%) + G 12.47 20.93 20.14(0.15%) A (0.15%) + B 2.87 6.27 9.32 (0.15%) E (0.15%) + B 6.05 14.0018.32 (0.15%) *A is bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, TINUVIN ® 123, CIBA). B is5-(4-trifluoromethylphenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,Compound of Example 2. C is2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, TINUVIN ® 329, CIBA.D is 4-octyloxy-2-hydroxybenzophenone, CHIMASSORB ® 81, CIBA. E is1,3,5-tris[N-cyclohexyl-N-(2,2,6,6-tetramethylpiperazin-3-on-4-yl)amino]-s-triazine,GOODRITE ® 3150, Goodrich. F is bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate, TINUVIN ® 292, CIBA. G is1,4-bis[2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazol-5-yl]benzene,Compound of Example 16.

These data show that a hindered amine in combination with an instant UVabsorber protects the white scented candle wax far better thanconventional UV absorbers or a hindered amine alone.

EXAMPLE 32 Color Fade of White Scented Candle Wax Under UV Lamp Exposure

A variety of different stabilizers are evaluated in white scented candlewax obtained from the Candle-Lite Corporation under UV lamp exposure.The ΔE values represent the change in color after the indicated days ofexposure. A low ΔE value indicates less change in color and is highlydesired.

ΔE after Sample* (wt % add) 5.9 days 16.6 days 35.0 days Blank (no add)42.90 45.57 45.14 A (0.3%) 34.65 36.64 35.07 F (0.3%) 35.55 33.80 29.30C (0.15%) + D 24.48 28.86 27.80 (0.15%) F (0.15%) + G 14.53 21.47 22.17(0.15%) A (0.15%) + B 7.71 10.57 12.97 (0.15%) E (0.15%) + B 9.01 14.0315.50 (0.15%) *A is bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, TINUVIN ® 123, CIBA). B is5-(4-trifluoromethylphenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,Compound of Example 2. C is2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, TINUVIN ® 329, CIBA.D is 4-octyloxy-2-hydroxybenzophenone, CHIMASSORB ® 81, CIBA. E is1,3,5-tris[N-cyclohexyl-N-(2,2,6,6-tetramethylpiperazin-3-on-4-yl)amino]-s-triazine,GOODRITE ® 3150, Goodrich. F is bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate, TINUVIN ® 292, CIBA. G is1,4-bis[2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazol-5-yl]benzene,Compound of Example 16.

These data show that a hindered amine in combination with an instant UVabsorber protects the white scented candle wax far better thanconventional UV absorbers or a hindered amine alone.

EXAMPLE 33

Spectral Properties of Substituted 5-Arylbenzotriazole UV Absorbers ofFormulas I and II

The following table shows the absorption maxima and molar extinctioncoefficients of a number of 2H-benzotriazole UV absorbers of formulas Iand II where E₁ is α-cumyl and E₂ is tert-octyl unless otherwiseindicated. A state-of-the-art commercial benzotriazole UV absorber,2-[2-hydroxy-3,5-di-(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole(TINUVIN® 900, CIBA) and a number of instant 5-aryl substitutedcompounds are tested. The concentrations of each of the samples areidentical, namely 20 mg/L in ethyl acetate. The absorption λ maxima ofthe instant compounds at 350 to 369 nm are red-shifted, i.e. shiftedtowards the visible relative to the commercial control, which has anabsorption λ maximum at 342 nm (ε 15,500). The molar extinctioncoefficients ε of the 5-aryl substituted compounds substituted instantcompounds far exceed that of the control compound at the absorption λmaxima.

Absorption Maxima and Molar Extinction Coefficients of Benzotriazole UVAbsorbers R or T Hammett Compound of nm Molar ε 5-Substitution ConstantControl* 342 (15,500) hydrogen σ_(p) = 0.0 Example 7 355 (17,745)3-trifluorophenyl σ_(m) = +0.46 Example 11 357 (19,727)3,5-bis-CF₃phenyl σ_(m) = +0.46 Example 8 350 (21,035) 2-trifluorophenylExample 15 362 (21,506) 5-methoxyphenyl σ_(p) = −0.27 Example 2 356(23,910) 4-trifluorophenyl σ_(p) = +0.53 Example 13 358 (23,981)4-cyanophenyl σ_(p) = +0.70 Example 10 356 (25,690) phenyl σ_(p) = 0.0Example 12 361 (31,903) 1,1′-biphenyl-4-yl σ_(p) = +0.05 Example 16**369 (52,629) p-phenylenebis Example 17*** 360 (25,453) 5-methoxyphenylσ_(p) = −0.27 *Control is2-[2-hydroxy-3,5-di-(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole,TINUVIN ®900, CIBA. **Example 16 is a compound of formula II where T isp-phenylene, E₁ is α-cumyl and E₂ is tert-octyl ***Example 17 is acompound of formula I where E₁ and E₂ are each tert-butyl.

1. A composition stabilized against thermal, oxidative or light-induceddegradation which comprises, (a) an organic material subject to thermal,oxidative or light-induced degradation, and (b) an effective stabilizingamount of a compound of formula

wherein T is a direct bond, 1,4-phenylene or said phenylene substitutedby one or two alkyl of 1 to 12 carbon atoms, E₁ is hydrogen, straight orbranched alkyl of 1 to 24 carbon atoms, phenylalkyl of 7 to 15 carbonatoms, phenyl, or said phenyl or said phenylalkyl substituted on thephenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms, and E₂ is straightor branched alkyl chain of 1 to 24 carbon atoms, straight or branchedchain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbonatoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl orsaid phenylalkyl substituted on the phenyl ring by 1 to 3 alkyl of 1 to4 carbon atoms; or E₂ is alkyl of 1 to 24 carbon atoms or alkenyl of 2to 18 carbon atoms substituted by one or more —OH, —OCOE₃, —NH₂, —NHCOE₃or —COOE₃, or mixtures thereof; or said alkyl or said alkenylinterrupted by one or more —O— which can be unsubstituted or substitutedby one or more —OH groups; where E₃ is hydrogen or alkyl of 1 to 24carbon atoms, and where said alkyl is interrupted by one or more —O— andwhich can be substituted by one or more —OH or —OR₂₁ groups where R₂₁ isalkyl of 1 to 12 carbon atoms.
 2. A composition according to claim 1wherein component (a) is a thermoplastic polyolefin, polyester,polyester urethane, polyether urethane or a water-borne coating.
 3. Acomposition according to claim 1 wherein component (a) is selected fromthe group consisting of polypropylene, thermoplastic polyolefin, lowdensity polyethylene, medium density polyethylene, high densitypolyethylene, linear low density polyethylene, poly(butene-1),ethylene/vinyl acetate copolymer, ethylene/propylene copolymer,copolymers of ethylene or propylene with other alpha-olefins, copolymersof acrylonitrile-butadiene-styrene (ABS), copolymers of acrylonitrileand styrene that are impact modified with ethylene-propylene rubber orethylene/propylene/alpha-olefin rubber or butyl acrylate rubber, blendsof ABS and polycarbonate, blends of ABS and poly(vinyl chloride) (PVC),poly(vinyl chloride), copolymers of styrene and butadiene (HIPS),copolymers of styrene and butadiene that also contain ethylene-propylenerubber or ethylene/propylene/alpha-olefin rubber or butyl acrylaterubber, thermoplastic elastomers and thermoplastic vulcanizates.
 4. Acomposition according to claim 1 wherein component (a) is a polyester orpolyether urethane or water-borne coating.
 5. A composition according toclaim 1 which additionally contains an effective stabilizing amount ofat least one coadditive stabilizer selected from the group consisting ofthe phenolic antioxidants, metal stearates, metal oxides,organophosphorus compounds, furanone antioxidants, hydroxylamines, UVabsorbers, non-NOR hindered amines, NOR hindered amines and mixturesthereof.
 6. A composition according to claim 1 which is a stabilizedstoving lacquer wherein component (a) is an acid catalyzed resin basedon hot crosslinkable, acrylic, acrylic melamine, polyester,polyurethane, polyamide or alkyd resin.
 7. A composition according toclaim 1 which additionally contains a UV absorber selected from thegroup consisting of the benzotriazoles, the s-triazines, the oxanilides,the salicylates, the hydroxybenzophenones, the benzoates and theα-cyanoacrylates.
 8. A composition according to claim 1 which is anenamel of high solids content for industrial finishes.
 9. A compositionaccording to claim 1 which is a finishing enamel for automobiles.
 10. Acomposition according to claim 1 wherein component (a) is a polyolefin,polycarbonate, a styrenic, ABS, a nylon (polyamide), a polyester, apolyurethane, a polyacrylate, a rubber modified styrenic, poly(vinylchloride), poly(vinyl butyral), polyacetal (polyoxymethylene), or otherblends or copolymers such as poly(ethylene/1,4-cyclohexylenedimethyleneterephthalate) PETG or an ethylene/acrylic acid copolymer or saltsthereof (an ionomer).
 11. A composition according to claim 10 whereinthe polymer is a polyester or a polyacrylate.
 12. A compositionaccording to claim 10 wherein the polyester is poly(ethyleneterephthalate), poly(butylene terephthalate) or poly(ethylenenaphthalenedicarboxylate), or copolymerpoly(ethylene/1,4-cyclohexylenedimethylene terephthalate) PETG.
 13. Acomposition according to claim 1 wherein component (a) is a polyolefinor polycarbonate.
 14. A composition according to claim 1 whereincomponent (a) is a photographic composition.
 15. A composition accordingto claim 1 wherein the organic material is a candle wax.
 16. Acomposition according to claim 15 wherein the candle wax additionallycontains an effective stabilizing amount of a hindered amine.